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A supercapacitor (SC), also called an ultracapacitor, is a high-capacity
capacitor A capacitor is a device that stores electrical energy in an electric field by virtue of accumulating electric charges on two close surfaces insulated from each other. It is a passive electronic component with two terminals. The effect of ...
, with a
capacitance Capacitance is the capability of a material object or device to store electric charge. It is measured by the change in charge in response to a difference in electric potential, expressed as the ratio of those quantities. Commonly recognized are ...
value much higher than other capacitors but with lower
voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to m ...
limits. It bridges the gap between
electrolytic capacitor An electrolytic capacitor is a polarized capacitor whose anode or positive plate is made of a metal that forms an insulating oxide layer through anodization. This oxide layer acts as the dielectric of the capacitor. A solid, liquid, or gel el ...
s and
rechargeable batteries A rechargeable battery, storage battery, or secondary cell (formally a type of energy accumulator), is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or prima ...
. It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more
charge and discharge cycle A charge cycle is the process of charging a rechargeable battery and discharging it as required into a load. The term is typically used to specify a battery's expected life, as the number of charge cycles affects life more than the mere passage of ...
s than
rechargeable batteries A rechargeable battery, storage battery, or secondary cell (formally a type of energy accumulator), is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or prima ...
. Supercapacitors are used in applications requiring many rapid charge/discharge cycles, rather than long-term compact energy storage — in automobiles, buses, trains, cranes and elevators, where they are used for
regenerative braking Regenerative braking is an energy recovery mechanism that slows down a moving vehicle or object by converting its kinetic energy into a form that can be either used immediately or stored until needed. In this mechanism, the electric traction mo ...
, short-term energy storage, or burst-mode power delivery. Smaller units are used as power backup for
static random-access memory Static random-access memory (static RAM or SRAM) is a type of random-access memory (RAM) that uses latching circuitry (flip-flop) to store each bit. SRAM is volatile memory; data is lost when power is removed. The term ''static'' differen ...
(SRAM). Unlike ordinary capacitors, supercapacitors do not use the conventional solid
dielectric In electromagnetism, a dielectric (or dielectric medium) is an electrical insulator that can be polarised by an applied electric field. When a dielectric material is placed in an electric field, electric charges do not flow through the mate ...
, but rather, they use
electrostatic Electrostatics is a branch of physics that studies electric charges at rest (static electricity). Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word for amber ...
double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
and
electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
pseudocapacitance Pseudocapacitance is the Electrochemistry, electrochemical storage of electricity in an Supercapacitor, electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible Faradaic current, fa ...
, both of which contribute to the total capacitance of the capacitor, with a few differences: * Electrostatic double-layer capacitors (EDLCs) use
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
s or derivatives with much higher electrostatic double-layer capacitance than electrochemical pseudocapacitance, achieving separation of charge in a
Helmholtz Hermann Ludwig Ferdinand von Helmholtz (31 August 1821 – 8 September 1894) was a German physicist and physician who made significant contributions in several scientific fields, particularly hydrodynamic stability. The Helmholtz Association, ...
double layer at the
interface Interface or interfacing may refer to: Academic journals * ''Interface'' (journal), by the Electrochemical Society * '' Interface, Journal of Applied Linguistics'', now merged with ''ITL International Journal of Applied Linguistics'' * '' Int ...
between the surface of a conductive electrode and an
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
. The separation of charge is of the order of a few
ångström The angstromEntry "angstrom" in the Oxford online dictionary. Retrieved on 2019-03-02 from https://en.oxforddictionaries.com/definition/angstrom.Entry "angstrom" in the Merriam-Webster online dictionary. Retrieved on 2019-03-02 from https://www.m ...
s (0.3–0.8  nm), much smaller than in a conventional capacitor. * Electrochemical pseudocapacitors use
metal oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
or
conducting polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage of conductive polymers ...
electrodes with a high amount of electrochemical pseudocapacitance additional to the double-layer capacitance. Pseudocapacitance is achieved by Faradaic
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...
charge-transfer with
redox reactions Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
, intercalation or electrosorption. * Hybrid capacitors, such as the
lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
, use electrodes with differing characteristics: one exhibiting mostly electrostatic capacitance and the other mostly electrochemical capacitance. The electrolyte forms an ionic conductive connection between the two electrodes which distinguishes them from conventional electrolytic capacitors where a dielectric layer always exists, and the so-called electrolyte, ''e.g.'', MnO2 or conducting polymer, is in fact part of the second electrode (the cathode, or more correctly the positive electrode). Supercapacitors are polarized by design with asymmetric electrodes, or, for symmetric electrodes, by a potential applied during manufacturing.


History

Development of the double layer and pseudocapacitance models (see
Double layer (interfacial) A double layer (DL, also called an electrical double layer, EDL) is a structure that appears on the surface of an object when it is exposed to a fluid. The object might be a solid particle, a gas bubble, a liquid droplet, or a porous body. The D ...
).


Evolution of components

In the early 1950s,
General Electric General Electric Company (GE) is an American multinational conglomerate founded in 1892, and incorporated in New York state and headquartered in Boston. The company operated in sectors including healthcare, aviation, power, renewable energ ...
engineers began experimenting with porous carbon electrodes in the design of capacitors, from the design of
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requ ...
s and
rechargeable batteries A rechargeable battery, storage battery, or secondary cell (formally a type of energy accumulator), is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or prima ...
.
Activated charcoal "Activated" is a song by English singer Cher Lloyd. It was released on 22 July 2016 through Vixen Records. The song was made available to stream exclusively on ''Rolling Stone'' a day before to release (on 21 July 2016). Background In an interv ...
is an
electrical conductor In physics and electrical engineering, a conductor is an object or type of material that allows the flow of charge (electric current) in one or more directions. Materials made of metal are common electrical conductors. Electric current is gener ...
that is an extremely porous "spongy" form of carbon with a high
specific surface area Specific surface area (SSA) is a property of solids defined as the total surface area of a material per unit of mass, (with units of m2/kg or m2/g) or solid or bulk volume (units of m2/m3 or m−1). It is a physical value that can be used to det ...
. In 1957 H. Becker developed a "Low voltage electrolytic capacitor with porous carbon electrodes". He believed that the energy was stored as a charge in the carbon pores as in the pores of the etched foils of electrolytic capacitors. Because the double layer mechanism was not known by him at the time, he wrote in the patent: "It is not known exactly what is taking place in the component if it is used for energy storage, but it leads to an extremely high capacity." General Electric did not immediately pursue this work. In 1966 researchers at Standard Oil of Ohio (SOHIO) developed another version of the component as "electrical energy storage apparatus", while working on experimental
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requ ...
designs.J. G. Schindall, The Change of the Ultra-Capacitors, IEEE Spectrum, November 200

/ref> The nature of electrochemical energy storage was not described in this patent. Even in 1970, the electrochemical capacitor patented by Donald L. Boos was registered as an electrolytic capacitor with activated carbon electrodes. Early electrochemical capacitors used two aluminum foils covered with activated carbon — the electrodes — that were soaked in an electrolyte and separated by a thin porous insulator. This design gave a capacitor with a capacitance on the order of one
farad The farad (symbol: F) is the unit of electrical capacitance, the ability of a body to store an electrical charge, in the International System of Units (SI). It is named after the English physicist Michael Faraday (1791–1867). In SI base unit ...
, significantly higher than electrolytic capacitors of the same dimensions. This basic mechanical design remains the basis of most electrochemical capacitors. SOHIO did not commercialize their invention, licensing the technology to
NEC is a Japanese multinational information technology and electronics corporation, headquartered in Minato, Tokyo. The company was known as the Nippon Electric Company, Limited, before rebranding in 1983 as NEC. It provides IT and network soluti ...
, who finally marketed the results as "supercapacitors" in 1978, to provide backup power for computer memory. Between 1975 and 1980 Brian Evans Conway conducted extensive fundamental and development work on
ruthenium oxide Ruthenium oxide may refer to either of the following: *Ruthenium(IV) oxide Ruthenium(IV) oxide is the inorganic compound with the formula Ru O2. This black solid is the most common oxide of ruthenium. It is widely used as an electrocatalyst fo ...
electrochemical capacitors. In 1991 he described the difference between "supercapacitor" and "battery" behaviour in electrochemical energy storage. In 1999 he defined the term "supercapacitor" to make reference to the increase in observed capacitance by surface redox reactions with faradaic charge transfer between electrodes and ions. His "supercapacitor" stored electrical charge partially in the Helmholtz double-layer and partially as result of faradaic reactions with "pseudocapacitance" charge transfer of electrons and protons between electrode and electrolyte. The working mechanisms of pseudocapacitors are redox reactions, intercalation and electrosorption (adsorption onto a surface). With his research, Conway greatly expanded the knowledge of electrochemical capacitors. The market expanded slowly. That changed around 1978 as
Panasonic formerly between 1935 and 2008 and the first incarnation of between 2008 and 2022, is a major Japanese multinational corporation, multinational Conglomerate (company), conglomerate corporation, headquartered in Kadoma, Osaka, Kadoma, Osaka P ...
marketed its Goldcaps brand.Panasonic, Electric Double Layer Capacitor, Technical guide,1. Introductio
Panasonic Goldcaps
This product became a successful energy source for memory backup applications. Competition started only years later. In 1987 ELNA "Dynacap"s entered the market. First generation EDLC's had relatively high
internal resistance A practical electrical power source which is a linear electric circuit may, according to Thévenin's theorem, be represented as an ideal voltage source in series with an impedance. This impedance is termed the internal resistance of the source. ...
that limited the discharge current. They were used for low current applications such as powering SRAM chips or for data backup. At the end of the 1980s, improved electrode materials increased capacitance values. At the same time, the development of electrolytes with better conductivity lowered the
equivalent series resistance Practical capacitors and inductors as used in electric circuits are not ideal components with only capacitance or inductance. However, they can be treated, to a very good degree of approximation, as being ideal capacitors and inductors in series ...
(ESR) increasing charge/discharge currents. The first supercapacitor with low internal resistance was developed in 1982 for military applications through the Pinnacle Research Institute (PRI), and were marketed under the brand name "PRI Ultracapacitor". In 1992, Maxwell Laboratories (later Maxwell Technologies) took over this development. Maxwell adopted the term Ultracapacitor from PRI and called them "Boost Caps" to underline their use for power applications. Since capacitors' energy content increases with the square of the voltage, researchers were looking for a way to increase the electrolyte's
breakdown voltage The breakdown voltage of an insulator is the minimum voltage that causes a portion of an insulator to experience electrical breakdown and become electrically conductive. For diodes, the breakdown voltage is the minimum reverse voltage that mak ...
. In 1994 using the
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
of a 200V high voltage
tantalum electrolytic capacitor A tantalum electrolytic capacitor is an electrolytic capacitor, a passive component of electronic circuits. It consists of a pellet of porous tantalum metal as an anode, covered by an insulating oxide layer that forms the dielectric, surrounded ...
, David A. Evans developed an "Electrolytic-Hybrid Electrochemical Capacitor". These capacitors combine features of electrolytic and electrochemical capacitors. They combine the high dielectric strength of an anode from an electrolytic capacitor with the high capacitance of a pseudocapacitive
metal oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of −2. Most of the E ...
(
ruthenium Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
(IV) oxide)
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in whi ...
from an electrochemical capacitor, yielding a hybrid electrochemical capacitor. Evans' capacitors, coined Capattery, had an energy content about a factor of 5 higher than a comparable tantalum electrolytic capacitor of the same size.David A. Evans
''The Littlest Big Capacitor - an Evans Hybrid''
Technical Paper, Evans Capacitor Company 2007
Their high costs limited them to specific military applications. Recent developments include
lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
s. These hybrid capacitors were pioneered by
Fujitsu is a Japanese multinational information and communications technology equipment and services corporation, established in 1935 and headquartered in Tokyo. Fujitsu is the world's sixth-largest IT services provider by annual revenue, and the la ...
's FDK in 2007. They combine an electrostatic carbon electrode with a pre-doped lithium-ion electrochemical electrode. This combination increases the capacitance value. Additionally, the pre-doping process lowers the anode potential and results in a high cell output voltage, further increasing specific energy. Research departments active in many companies and universities are working to improve characteristics such as specific energy, specific power, and cycle stability and to reduce production costs.


Design


Basic design

Electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
capacitors (supercapacitors) consist of two electrodes separated by an ion-permeable membrane ( separator), and an electrolyte ionically connecting both electrodes. When the electrodes are polarized by an applied voltage, ions in the electrolyte form electric double layers of opposite polarity to the electrode's polarity. For example, positively polarized electrodes will have a layer of negative ions at the electrode/electrolyte interface along with a charge-balancing layer of positive ions adsorbing onto the negative layer. The opposite is true for the negatively polarized electrode. Additionally, depending on electrode material and surface shape, some ions may permeate the double layer becoming specifically adsorbed ions and contribute with pseudocapacitance to the total capacitance of the supercapacitor.


Capacitance distribution

The two electrodes form a series circuit of two individual capacitors ''C''1 and ''C''2. The total capacitance ''C''total is given by the formula :C_\text = \frac Supercapacitors may have either symmetric or asymmetric electrodes. Symmetry implies that both electrodes have the same capacitance value, yielding a total capacitance of half the value of each single electrode (if ''C''1 = ''C''2, then ''C''total = ½ ''C''1). For asymmetric capacitors, the total capacitance can be taken as that of the electrode with the smaller capacitance (if ''C''1 >> ''C''2, then ''C''total ≈ ''C''2).


Storage principles

Electrochemical capacitors use the double-layer effect to store electric energy; however, this double-layer has no conventional solid dielectric to separate the charges. There are two storage principles in the electric double-layer of the electrodes that contribute to the total capacitance of an electrochemical capacitor: *
Double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
,
electrostatic Electrostatics is a branch of physics that studies electric charges at rest (static electricity). Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word for amber ...
storage of the electrical energy achieved by separation of charge in a Helmholtz double layer. *
Pseudocapacitance Pseudocapacitance is the Electrochemistry, electrochemical storage of electricity in an Supercapacitor, electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible Faradaic current, fa ...
,
electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
storage of the electrical energy achieved by faradaic
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
reactions with charge-transfer. Both capacitances are only separable by measurement techniques. The amount of charge stored per unit voltage in an electrochemical capacitor is primarily a function of the electrode size, although the amount of capacitance of each storage principle can vary extremely.


Electrical double-layer capacitance

Every electrochemical capacitor has two electrodes, mechanically separated by a separator, which are ionically connected to each other via the
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
. The electrolyte is a mixture of positive and negative ions dissolved in a solvent such as water. At each of the two electrode surfaces originates an area in which the liquid electrolyte contacts the conductive metallic surface of the electrode. This interface forms a common boundary among two different phases of matter, such as an insoluble
solid Solid is one of the State of matter#Four fundamental states, four fundamental states of matter (the others being liquid, gas, and Plasma (physics), plasma). The molecules in a solid are closely packed together and contain the least amount o ...
electrode surface and an adjacent
liquid A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume independent of pressure. As such, it is one of the four fundamental states of matter (the others being solid, gas, a ...
electrolyte. In this interface occurs a very special phenomenon of the double layer effect. Applying a voltage to an electrochemical capacitor causes both electrodes in the capacitor to generate electrical double-layers. These double-layers consist of two layers of charges: one electronic layer is in the surface lattice structure of the electrode, and the other, with opposite polarity, emerges from dissolved and solvated ions in the electrolyte. The two layers are separated by a monolayer of solvent
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
s, ''e.g.'', for
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
as
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
by water molecules, called inner Helmholtz plane (IHP). Solvent molecules adhere by
physical adsorption Physisorption, also called physical adsorption, is a process in which the electronic structure of the atom or molecule is barely perturbed upon adsorption. Overview The fundamental interacting force of physisorption is Van der Waals force. Even ...
on the surface of the electrode and separate the oppositely polarized ions from each other, and can be idealised as a molecular dielectric. In the process, there is no transfer of charge between electrode and electrolyte, so the forces that cause the adhesion are not chemical bonds, but physical forces, ''e.g.'', electrostatic forces. The adsorbed molecules are polarized, but, due to the lack of transfer of charge between electrolyte and electrode, suffered no chemical changes. The amount of charge in the electrode is matched by the magnitude of counter-charges in outer Helmholtz plane (OHP). This double-layer phenomena stores electrical charges as in a conventional capacitor. The double-layer charge forms a static electric field in the molecular layer of the solvent molecules in the IHP that corresponds to the strength of the applied voltage. The double-layer serves approximately as the dielectric layer in a conventional capacitor, albeit with the thickness of a single molecule. Thus, the standard formula for conventional plate capacitors can be used to calculate their capacitance: :C= \varepsilon\frac. Accordingly, capacitance ''C'' is greatest in capacitors made from materials with a high
permittivity In electromagnetism, the absolute permittivity, often simply called permittivity and denoted by the Greek letter ''ε'' ( epsilon), is a measure of the electric polarizability of a dielectric. A material with high permittivity polarizes more in ...
''ε'', large electrode plate surface areas ''A'' and small distance between plates ''d''. As a result, double-layer capacitors have much higher capacitance values than conventional capacitors, arising from the extremely large surface area of activated carbon electrodes and the extremely thin double-layer distance on the order of a few
ångström The angstromEntry "angstrom" in the Oxford online dictionary. Retrieved on 2019-03-02 from https://en.oxforddictionaries.com/definition/angstrom.Entry "angstrom" in the Merriam-Webster online dictionary. Retrieved on 2019-03-02 from https://www.m ...
s (0.3-0.8 nm), of order of the
Debye length In plasmas and electrolytes, the Debye length \lambda_ (also called Debye radius), is a measure of a charge carrier's net electrostatic effect in a solution and how far its electrostatic effect persists. With each Debye length the charges are in ...
. The main drawback of carbon electrodes of double-layer SCs is small values of quantum capacitance which act in series with capacitance of ionic space charge. Therefore, further increase of density of capacitance in SCs can be connected with increasing of quantum capacitance of carbon electrode nanostructures. The amount of charge stored per unit voltage in an electrochemical capacitor is primarily a function of the electrode size. The electrostatic storage of energy in the double-layers is linear with respect to the stored charge, and correspond to the concentration of the adsorbed ions. Also, while charge in conventional capacitors is transferred via electrons, capacitance in double-layer capacitors is related to the limited moving speed of ions in the electrolyte and the resistive porous structure of the electrodes. Since no chemical changes take place within the electrode or electrolyte, charging and discharging electric double-layers in principle is unlimited. Real supercapacitors lifetimes are only limited by electrolyte evaporation effects.


Electrochemical pseudocapacitance

Applying a voltage at the electrochemical capacitor terminals moves electrolyte ions to the opposite polarized electrode and forms a double-layer in which a single layer of
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
molecules acts as separator. Pseudocapacitance can originate when specifically adsorbed ions out of the electrolyte pervade the double-layer. This pseudocapacitance stores electrical energy by means of reversible faradaic
redox reactions Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
on the surface of suitable electrodes in an electrochemical capacitor with an electric double-layer. Pseudocapacitance is accompanied with an
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have no kn ...
charge-transfer between
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
and electrode coming from a de-solvated and
adsorbed Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a ...
ion whereby only one electron per charge unit is participating. This faradaic charge transfer originates by a very fast sequence of reversible redox, intercalation or electrosorption processes. The adsorbed ion has no
chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the pos ...
with the atoms of the electrode (no chemical bonds arise) since only a charge-transfer take place. The electrons involved in the faradaic processes are transferred to or from
valence electron In chemistry and physics, a valence electron is an electron in the outer shell associated with an atom, and that can participate in the formation of a chemical bond if the outer shell is not closed. In a single covalent bond, a shared pair forms ...
states ( orbitals) of the redox electrode reagent. They enter the negative electrode and flow through the external circuit to the positive electrode where a second double-layer with an equal number of anions has formed. The electrons reaching the positive electrode are not transferred to the anions forming the double-layer, instead they remain in the strongly ionized and "electron hungry" transition-metal ions of the electrode's surface. As such, the storage capacity of faradaic pseudocapacitance is limited by the finite quantity of
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
in the available surface. A faradaic pseudocapacitance only occurs together with a static
double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
, and its magnitude may exceed the value of double-layer capacitance for the same surface area by factor 100, depending on the nature and the structure of the electrode, because all the pseudocapacitance reactions take place only with de-solvated ions, which are much smaller than solvated ion with their solvating shell. The amount of pseudocapacitance has a linear function within narrow limits determined by the potential-dependent degree of surface coverage of the adsorbed anions. The ability of electrodes to accomplish pseudocapacitance effects by redox reactions, intercalation or electrosorption strongly depends on the chemical affinity of electrode materials to the ions adsorbed on the electrode surface as well as on the structure and dimension of the electrode pores. Materials exhibiting redox behavior for use as electrodes in pseudocapacitors are transition-metal oxides like RuO2, IrO2, or MnO2 inserted by doping in the conductive electrode material such as active carbon, as well as conducting polymers such as
polyaniline Polyaniline (PANI) is a conducting polymer and organic semiconductor of the semi-flexible rod polymer family. The compound has been of interest since the 1980s because of its electrical conductivity and mechanical properties. Polyaniline is one of ...
or derivatives of
polythiophene Polythiophenes (PTs) are polymerized thiophenes, a sulfur heterocyclic compound, heterocycle. The parent PT is an insoluble colored solid with the formula (C4H2S)n. The rings are linked through the 2- and 5-positions. Poly(alkylthiophene)s hav ...
covering the electrode material. The amount of
electric charge Electric charge is the physical property of matter that causes charged matter to experience a force when placed in an electromagnetic field. Electric charge can be ''positive'' or ''negative'' (commonly carried by protons and electrons respe ...
stored in a pseudocapacitance is linearly proportional to the applied
voltage Voltage, also known as electric pressure, electric tension, or (electric) potential difference, is the difference in electric potential between two points. In a static electric field, it corresponds to the work needed per unit of charge to m ...
. The unit of pseudocapacitance is
farad The farad (symbol: F) is the unit of electrical capacitance, the ability of a body to store an electrical charge, in the International System of Units (SI). It is named after the English physicist Michael Faraday (1791–1867). In SI base unit ...
.


Potential distribution

Conventional
capacitor A capacitor is a device that stores electrical energy in an electric field by virtue of accumulating electric charges on two close surfaces insulated from each other. It is a passive electronic component with two terminals. The effect of ...
s (also known as electrostatic capacitors), such as
ceramic capacitor A ceramic capacitor is a fixed-value capacitor where the ceramic material acts as the dielectric. It is constructed of two or more alternating layers of ceramic and a metal layer acting as the electrodes. The composition of the ceramic material de ...
s and
film capacitor Film capacitors, plastic film capacitors, film dielectric capacitors, or polymer film capacitors, generically called film caps as well as power film capacitors, are electrical capacitors with an insulating plastic film as the dielectric, sometime ...
s, consist of two electrodes separated by a
dielectric In electromagnetism, a dielectric (or dielectric medium) is an electrical insulator that can be polarised by an applied electric field. When a dielectric material is placed in an electric field, electric charges do not flow through the mate ...
material. When charged, the energy is stored in a
static Static may refer to: Places *Static Nunatak, a nunatak in Antarctica United States * Static, Kentucky and Tennessee *Static Peak, a mountain in Wyoming **Static Peak Divide, a mountain pass near the peak Science and technology Physics *Static el ...
electric field An electric field (sometimes E-field) is the physical field that surrounds electrically charged particles and exerts force on all other charged particles in the field, either attracting or repelling them. It also refers to the physical field fo ...
that permeates the dielectric between the electrodes. The total energy increases with the amount of stored charge, which in turn correlates linearly with the potential (voltage) between the plates. The maximum potential difference between the plates (the maximal voltage) is limited by the dielectric's breakdown field strength. The same static storage also applies for
electrolytic capacitor An electrolytic capacitor is a polarized capacitor whose anode or positive plate is made of a metal that forms an insulating oxide layer through anodization. This oxide layer acts as the dielectric of the capacitor. A solid, liquid, or gel el ...
s in which most of the potential decreases over the
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
's thin oxide layer. The somewhat resistive liquid electrolyte (
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in whi ...
) accounts for a small decrease of potential for "wet" electrolytic capacitors, while electrolytic capacitors with solid conductive polymer electrolyte this voltage drop is negligible. In contrast,
electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outc ...
capacitors (supercapacitors) consists of two electrodes separated by an ion-permeable membrane (separator) and electrically connected via an electrolyte. Energy storage occurs within the double-layers of both electrodes as a mixture of a double-layer capacitance and pseudocapacitance. When both electrodes have approximately the same resistance (
internal resistance A practical electrical power source which is a linear electric circuit may, according to Thévenin's theorem, be represented as an ideal voltage source in series with an impedance. This impedance is termed the internal resistance of the source. ...
), the potential of the capacitor decreases symmetrically over both double-layers, whereby a voltage drop across the equivalent series resistance (ESR) of the electrolyte is achieved. For asymmetrical supercapacitors like hybrid capacitors the voltage drop between the electrodes could be asymmetrical. The maximum potential across the capacitor (the maximal voltage) is limited by the electrolyte decomposition voltage. Both electrostatic and electrochemical energy storage in supercapacitors are linear with respect to the stored charge, just as in conventional capacitors. The voltage between the capacitor terminals is linear with respect to the amount of stored energy. Such linear voltage gradient differs from rechargeable electrochemical batteries, in which the voltage between the terminals remains independent of the amount of stored energy, providing a relatively constant voltage.


Comparison with other storage technologies

Supercapacitors compete with electrolytic capacitors and rechargeable batteries, especially
lithium-ion batteries A lithium-ion or Li-ion battery is a type of rechargeable battery which uses the reversible reduction of lithium ions to store energy. It is the predominant battery type used in portable consumer electronics and electric vehicles. It also se ...
. The following table compares the major parameters of the three main supercapacitor families with electrolytic capacitors and batteries. Electrolytic capacitors feature nearly unlimited charge/discharge cycles, high dielectric strength (up to 550 V) and good frequency response as
alternating current Alternating current (AC) is an electric current which periodically reverses direction and changes its magnitude continuously with time in contrast to direct current (DC) which flows only in one direction. Alternating current is the form in whic ...
(AC) reactance in the lower frequency range. Supercapacitors can store 10 to 100 times more energy than electrolytic capacitors, but they do not support AC applications. With regards to rechargeable batteries, supercapacitors feature higher peak currents, low cost per cycle, no danger of overcharging, good reversibility, non-corrosive electrolyte and low material toxicity. Batteries offer lower purchase cost and stable voltage under discharge, but require complex electronic control and switching equipment, with consequent energy loss and spark hazard given a short.


Styles

Supercapacitors are made in different styles, such as flat with a single pair of electrodes, wound in a cylindrical case, or stacked in a rectangular case. Because they cover a broad range of capacitance values, the size of the cases can vary. File:Supercap-flat-case.jpg, Flat style of a supercapacitor used for mobile components File:Polarität-EDLC-P1070160.JPG, Radial style of a lithium-ion type supercapacitor for PCB mounting used for industrial applications


Construction details

File:Electric double-layer capacitor (Activated carbon electrode - Tube type).PNG, Schematic construction of a wound supercapacitor
1. terminals, 2. safety vent, 3. sealing disc, 4. aluminum can, 5. positive pole, 6. separator, 7. carbon electrode, 8. collector, 9. carbon electrode, 10. negative pole File:Electric double-layer capacitor (Activated carbon electrode - BOX type).PNG, Schematic construction of a supercapacitor with stacked electrodes
1. positive electrode, 2. negative electrode, 3. separator
Supercapacitors are constructed with two metal foils (current collectors), each coated with an electrode material such as activated carbon, which serve as the power connection between the electrode material and the external terminals of the capacitor. Specifically to the electrode material is a very large surface area. In this example the activated carbon is electrochemically etched, so that the surface area of the material is about 100,000 times greater than the smooth surface. The electrodes are kept apart by an ion-permeable membrane (separator) used as an insulator to protect the electrodes against
short circuit A short circuit (sometimes abbreviated to short or s/c) is an electrical circuit that allows a current to travel along an unintended path with no or very low electrical impedance. This results in an excessive current flowing through the circuit ...
s. This construction is subsequently rolled or folded into a cylindrical or rectangular shape and can be stacked in an aluminum can or an adaptable rectangular housing. The cell is then impregnated with a liquid or viscous electrolyte of organic or aqueous type. The electrolyte, an ionic conductor, enters the pores of the electrodes and serves as the conductive connection between the electrodes across the separator. Finally, the housing is hermetically sealed to ensure stable behavior over the specified lifetime.


Types

Electrical energy is stored in supercapacitors via two storage principles, static
double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
and electrochemical
pseudocapacitance Pseudocapacitance is the Electrochemistry, electrochemical storage of electricity in an Supercapacitor, electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible Faradaic current, fa ...
; and the distribution of the two types of capacitance depends on the material and structure of the electrodes. There are three types of supercapacitors based on storage principle: * Double-layer capacitors (EDLCs) — with activated carbon electrodes or derivatives with much higher electrostatic double-layer capacitance than electrochemical pseudocapacitance * Pseudocapacitors — with
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
oxide or
conducting polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage of conductive polymers ...
electrodes with a high electrochemical pseudocapacitance * Hybrid capacitors — with asymmetric electrodes, one of which exhibits mostly electrostatic and the other mostly electrochemical capacitance, such as
lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
s Because double-layer capacitance and pseudocapacitance both contribute inseparably to the total capacitance value of an electrochemical capacitor, a correct description of these capacitors only can be given under the generic term. The concepts of supercapattery and supercabattery have been recently proposed to better represent those hybrid devices that behave more like the supercapacitor and the rechargeable battery, respectively. The
capacitance Capacitance is the capability of a material object or device to store electric charge. It is measured by the change in charge in response to a difference in electric potential, expressed as the ratio of those quantities. Commonly recognized are ...
value of a supercapacitor is determined by two storage principles: *
Double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
 –
electrostatic Electrostatics is a branch of physics that studies electric charges at rest (static electricity). Since classical times, it has been known that some materials, such as amber, attract lightweight particles after rubbing. The Greek word for amber ...
storage of the electrical
energy In physics, energy (from Ancient Greek: ἐνέργεια, ''enérgeia'', “activity”) is the quantitative property that is transferred to a body or to a physical system, recognizable in the performance of work and in the form of heat a ...
achieved by separation of
charge Charge or charged may refer to: Arts, entertainment, and media Films * '' Charge, Zero Emissions/Maximum Speed'', a 2011 documentary Music * ''Charge'' (David Ford album) * ''Charge'' (Machel Montano album) * ''Charge!!'', an album by The Aqu ...
in a
Helmholtz Hermann Ludwig Ferdinand von Helmholtz (31 August 1821 – 8 September 1894) was a German physicist and physician who made significant contributions in several scientific fields, particularly hydrodynamic stability. The Helmholtz Association, ...
double layer at the
interface Interface or interfacing may refer to: Academic journals * ''Interface'' (journal), by the Electrochemical Society * '' Interface, Journal of Applied Linguistics'', now merged with ''ITL International Journal of Applied Linguistics'' * '' Int ...
between the
surface A surface, as the term is most generally used, is the outermost or uppermost layer of a physical object or space. It is the portion or region of the object that can first be perceived by an observer using the senses of sight and touch, and is ...
of a conductor
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials de ...
and an electrolytic solution
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
. The separation of charge distance in a double-layer is on the order of a few
ångström The angstromEntry "angstrom" in the Oxford online dictionary. Retrieved on 2019-03-02 from https://en.oxforddictionaries.com/definition/angstrom.Entry "angstrom" in the Merriam-Webster online dictionary. Retrieved on 2019-03-02 from https://www.m ...
s (0.3–0.8  nm) and is
static Static may refer to: Places *Static Nunatak, a nunatak in Antarctica United States * Static, Kentucky and Tennessee *Static Peak, a mountain in Wyoming **Static Peak Divide, a mountain pass near the peak Science and technology Physics *Static el ...
in origin. *
Pseudocapacitance Pseudocapacitance is the Electrochemistry, electrochemical storage of electricity in an Supercapacitor, electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible Faradaic current, fa ...
 – Electrochemical storage of the electrical energy, achieved by
redox reactions Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...
, electrosorption or intercalation on the surface of the electrode by specifically adsorbed
ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conve ...
s, that results in a reversible faradaic charge-transfer on the electrode. Double-layer capacitance and pseudocapacitance both contribute inseparably to the total capacitance value of a supercapacitor. However, the ratio of the two can vary greatly, depending on the design of the electrodes and the composition of the electrolyte. Pseudocapacitance can increase the capacitance value by as much as a factor of ten over that of the double-layer by itself. Electric double-layer capacitors (EDLC) are electrochemical capacitors in which energy storage predominantly is achieved by double-layer capacitance. In the past, all electrochemical capacitors were called "double-layer capacitors". Contemporary usage sees double-layer capacitors, together with pseudocapacitors, as part of a larger family of electrochemical capacitors called supercapacitors. They are also known as ultracapacitors.


Materials

The properties of supercapacitors come from the interaction of their internal materials. Especially, the combination of electrode material and type of electrolyte determine the functionality and thermal and electrical characteristics of the capacitors.


Electrodes

Supercapacitor electrodes are generally thin coatings applied and electrically connected to a conductive, metallic
current Currents, Current or The Current may refer to: Science and technology * Current (fluid), the flow of a liquid or a gas ** Air current, a flow of air ** Ocean current, a current in the ocean *** Rip current, a kind of water current ** Current (stre ...
collector. Electrodes must have good conductivity, high temperature stability, long-term chemical stability ( inertness), high corrosion resistance and high surface areas per unit volume and mass. Other requirements include environmental friendliness and low cost. The amount of double-layer as well as pseudocapacitance stored per unit voltage in a supercapacitor is predominantly a function of the electrode surface area. Therefore, supercapacitor electrodes are typically made of porous, spongy material with an extraordinarily high
specific surface area Specific surface area (SSA) is a property of solids defined as the total surface area of a material per unit of mass, (with units of m2/kg or m2/g) or solid or bulk volume (units of m2/m3 or m−1). It is a physical value that can be used to det ...
, such as activated carbon. Additionally, the ability of the electrode material to perform faradaic charge transfers enhances the total capacitance. Generally the smaller the electrode's pores, the greater the capacitance and
specific energy Specific energy or massic energy is energy per unit mass. It is also sometimes called gravimetric energy density, which is not to be confused with energy density, which is defined as energy per unit volume. It is used to quantify, for example, sto ...
. However, smaller pores increase
equivalent series resistance Practical capacitors and inductors as used in electric circuits are not ideal components with only capacitance or inductance. However, they can be treated, to a very good degree of approximation, as being ideal capacitors and inductors in series ...
(ESR) and decrease
specific power Power-to-weight ratio (PWR, also called specific power, or power-to-mass ratio) is a calculation commonly applied to engines and mobile power sources to enable the comparison of one unit or design to another. Power-to-weight ratio is a measuremen ...
. Applications with high peak currents require larger pores and low internal losses, while applications requiring high specific energy need small pores.


Electrodes for EDLCs

The most commonly used electrode material for supercapacitors is carbon in various manifestations such as activated carbon (AC), carbon fibre-cloth (AFC),
carbide-derived carbon Carbide-derived carbon (CDC), also known as tunable nanoporous carbon, is the common term for carbon materials derived from carbide precursors, such as binary (e.g. SiC, TiC), or ternary carbides, also known as MAX phases (e.g., Ti2AlC, Ti3SiC2). CD ...
(CDC), carbon
aerogel Aerogels are a class of synthetic porous ultralight material derived from a gel, in which the liquid component for the gel has been replaced with a gas, without significant collapse of the gel structure. The result is a solid with extremely low ...
,
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
(
graphene Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure.
),
graphane Graphane is a two-dimensional polymer of carbon and hydrogen with the formula unit (CH)n where ''n'' is large. Partial hydrogenation results in hydrogenated graphene, which was reported by Elias et al in 2009 by a TEM study to be "direct evidence ...
and
carbon nanotube A scanning tunneling microscopy image of a single-walled carbon nanotube Rotating single-walled zigzag carbon nanotube A carbon nanotube (CNT) is a tube made of carbon with diameters typically measured in nanometers. ''Single-wall carbon na ...
s (CNTs). Carbon-based electrodes exhibit predominantly static double-layer capacitance, even though a small amount of pseudocapacitance may also be present depending on the pore size distribution. Pore sizes in carbons typically range from
micropores A microporous material is a material containing pores with diameters less than 2 nm. Examples of microporous materials include zeolites and metal-organic frameworks. Porous materials are classified into several kinds by their size. The recom ...
(less than 2 nm) to mesopores (2-50 nm), but only micropores (<2 nm) contribute to pseudocapacitance. As pore size approaches the solvation shell size, solvent molecules are excluded and only unsolvated ions fill the pores (even for large ions), increasing ionic packing density and storage capability by faradaic intercalation.


= Activated carbon

= Activated carbon was the first material chosen for EDLC electrodes. Even though its electrical conductivity is approximately 0.003% that of metals ( 1,250 to 2,000 S/m), it is sufficient for supercapacitors. Activated carbon is an extremely porous form of carbon with a high
specific surface area Specific surface area (SSA) is a property of solids defined as the total surface area of a material per unit of mass, (with units of m2/kg or m2/g) or solid or bulk volume (units of m2/m3 or m−1). It is a physical value that can be used to det ...
— a common approximation is that 1 gram (0.035 oz) (a pencil-eraser-sized amount) has a surface area of roughly — about the size of 4 to 12
tennis court A tennis court is the venue where the sport of tennis is played. It is a firm rectangular surface with a low net stretched across the centre. The same surface can be used to play both doubles and singles matches. A variety of surfaces can be u ...
s. The bulk form used in electrodes is low-density with many pores, giving high double-layer capacitance. Solid activated carbon, also termed ''consolidated
amorphous carbon Amorphous carbon is free, reactive carbon that has no crystalline structure. Amorphous carbon materials may be stabilized by terminating dangling-π bonds with hydrogen. As with other amorphous solids, some short-range order can be observed. Amor ...
'' (CAC) is the most used electrode material for supercapacitors and may be cheaper than other carbon derivatives. It is produced from activated carbon powder pressed into the desired shape, forming a block with a wide distribution of pore sizes. An electrode with a surface area of about 1000 m2/g results in a typical double-layer capacitance of about 10 μF/cm2 and a specific capacitance of 100 F/g. virtually all commercial supercapacitors use powdered activated carbon made from coconut shells. Coconut shells produce activated carbon with more micropores than does charcoal made from wood.


= Activated carbon fibres

= Activated carbon fibres (ACF) are produced from activated carbon and have a typical diameter of 10 µm. They can have micropores with a very narrow pore-size distribution that can be readily controlled. The surface area of ACF woven into a textile is about . Advantages of ACF electrodes include low electrical resistance along the fibre axis and good contact to the collector. As for activated carbon, ACF electrodes exhibit predominantly double-layer capacitance with a small amount of pseudocapacitance due to their micropores.


= Carbon aerogel

= Carbon
aerogel Aerogels are a class of synthetic porous ultralight material derived from a gel, in which the liquid component for the gel has been replaced with a gas, without significant collapse of the gel structure. The result is a solid with extremely low ...
is a highly porous, synthetic,
ultralight material Ultralight materials are solids with a density of less than 10 mg/cm3, including silica aerogels, carbon nanotube aerogels, aerographite, metallic foams, polymeric foams, and metallic microlattices. The density of air is about 1.275 mg/ ...
derived from an organic gel in which the liquid component of the gel has been replaced with a gas. Aerogel electrodes are made via
pyrolysis The pyrolysis (or devolatilization) process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere. It involves a change of chemical composition. The word is coined from the Greek-derived elements ''py ...
of
resorcinol Resorcinol (or resorcin) is an organic compound with the formula C6H4(OH)2. It is one of three isomeric benzenediols, the 1,3-isomer (or '' meta''-isomer). Resorcinol crystallizes from benzene as colorless needles that are readily soluble in w ...
-
formaldehyde Formaldehyde ( , ) (systematic name methanal) is a naturally occurring organic compound with the formula and structure . The pure compound is a pungent, colourless gas that polymerises spontaneously into paraformaldehyde (refer to section F ...
aerogels and are more conductive than most activated carbons. They enable thin and mechanically stable electrodes with a thickness in the range of several hundred
micrometre The micrometre ( international spelling as used by the International Bureau of Weights and Measures; SI symbol: μm) or micrometer (American spelling), also commonly known as a micron, is a unit of length in the International System of Unit ...
s (µm) and with uniform pore size. Aerogel electrodes also provide mechanical and vibration stability for supercapacitors used in high-vibration environments. Researchers have created a carbon aerogel electrode with
gravimetric Gravimetry is the measurement of the strength of a gravitational field. Gravimetry may be used when either the magnitude of a gravitational field or the properties of matter responsible for its creation are of interest. Units of measurement G ...
densities of about 400–1200 m2/g and volumetric capacitance of 104 F/cm3, yielding a specific energy of () and specific power of . Standard aerogel electrodes exhibit predominantly double-layer capacitance. Aerogel electrodes that incorporate
composite material A composite material (also called a composition material or shortened to composite, which is the common name) is a material which is produced from two or more constituent materials. These constituent materials have notably dissimilar chemical or ...
can add a high amount of pseudocapacitance.


= Carbide-derived carbon

=
Carbide-derived carbon Carbide-derived carbon (CDC), also known as tunable nanoporous carbon, is the common term for carbon materials derived from carbide precursors, such as binary (e.g. SiC, TiC), or ternary carbides, also known as MAX phases (e.g., Ti2AlC, Ti3SiC2). CD ...
(CDC), also known as tunable nanoporous carbon, is a family of carbon materials derived from
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of the ...
precursors, such as binary
silicon carbide Silicon carbide (SiC), also known as carborundum (), is a hard chemical compound containing silicon and carbon. A semiconductor, it occurs in nature as the extremely rare mineral moissanite, but has been mass-produced as a powder and crystal sin ...
and
titanium carbide Titanium carbide, Ti C, is an extremely hard ( Mohs 9–9.5) refractory ceramic material, similar to tungsten carbide. It has the appearance of black powder with the sodium chloride ( face-centered cubic) crystal structure. It occurs in natur ...
, that are transformed into pure carbon via physical, ''e.g.'',
thermal decomposition Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is req ...
or chemical, ''e.g.'', halogenation) processes. Carbide-derived carbons can exhibit high surface area and tunable pore diameters (from micropores to mesopores) to maximize ion confinement, increasing pseudocapacitance by faradaic adsorption treatment. CDC electrodes with tailored pore design offer as much as 75% greater specific energy than conventional activated carbons. , a CDC supercapacitor offered a specific energy of 10.1 Wh/kg, 3,500 F capacitance and over one million charge-discharge cycles.


= Graphene

=
Graphene Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure.
is a one-atom thick sheet of
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on large ...
, with atoms arranged in a regular hexagonal pattern, also called "nanocomposite paper". Graphene has a theoretical specific surface area of 2630 m2/g which can theoretically lead to a capacitance of 550 F/g. In addition, an advantage of graphene over activated carbon is its higher electrical conductivity. a new development used graphene sheets directly as electrodes without collectors for portable applications. In one embodiment, a graphene-based supercapacitor uses curved graphene sheets that do not stack face-to-face, forming mesopores that are accessible to and wettable by ionic electrolytes at voltages up to 4 V. A specific energy of () is obtained at room temperature equaling that of a conventional
nickel metal hydride battery Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow to ...
, but with 100-1000 times greater specific power. The two-dimensional structure of graphene improves charging and discharging. Charge carriers in vertically oriented sheets can quickly migrate into or out of the deeper structures of the electrode, thus increasing currents. Such capacitors may be suitable for 100/120 Hz filter applications, which are unreachable for supercapacitors using other carbon materials.


= Carbon nanotubes

=
Carbon nanotube A scanning tunneling microscopy image of a single-walled carbon nanotube Rotating single-walled zigzag carbon nanotube A carbon nanotube (CNT) is a tube made of carbon with diameters typically measured in nanometers. ''Single-wall carbon na ...
s (CNTs), also called buckytubes, are
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
s with a cylindrical
nanostructure A nanostructure is a structure of intermediate size between microscopic and molecular structures. Nanostructural detail is microstructure at nanoscale. In describing nanostructures, it is necessary to differentiate between the number of dimens ...
. They have a hollow structure with walls formed by one-atom-thick sheets of graphite. These sheets are rolled at specific and discrete ("chiral") angles, and the combination of chiral angle and radius controls properties such as electrical conductivity, electrolyte wettability and ion access. Nanotubes are categorized as single-walled nanotubes (SWNTs) or multi-walled nanotubes (MWNTs). The latter have one or more outer tubes successively enveloping a SWNT, much like the Russian
matryoshka doll Matryoshka dolls ( ; rus, матрёшка, p=mɐˈtrʲɵʂkə, a=Ru-матрёшка.ogg), also known as stacking dolls, nesting dolls, Russian tea dolls, or Russian dolls, are a set of wooden dolls of decreasing size placed one inside ano ...
s. SWNTs have diameters ranging between 1 and 3 nm. MWNTs have thicker
coaxial In geometry, coaxial means that several three-dimensional linear or planar forms share a common axis. The two-dimensional analog is ''concentric''. Common examples: A coaxial cable is a three-dimensional linear structure. It has a wire conduc ...
walls, separated by spacing (0.34 nm) that is close to graphene's interlayer distance. Nanotubes can grow vertically on the collector substrate, such as a silicon wafer. Typical lengths are 20 to 100 µm. Carbon nanotubes can greatly improve capacitor performance, due to the highly wettable surface area and high conductivity. A SWNT-based supercapacitor with aqueous electrolyte was systematically studied at University of Delaware in Prof. Bingqing Wei's group. Li et al., for the first time, discovered that the ion-size effect and the electrode-electrolyte wettability are the dominant factors affecting the electrochemical behavior of flexible SWCNTs-supercapacitors in different 1 molar aqueous electrolytes with different anions and cations. The experimental results also showed for flexible supercapacitor that it is suggested to put enough pressure between the two electrodes to improve the aqueous electrolyte CNT supercapacitor. CNTs can store about the same charge as activated carbon per unit surface area, but nanotubes' surface is arranged in a regular pattern, providing greater wettability. SWNTs have a high theoretical specific surface area of 1315 m2/g, while that for MWNTs is lower and is determined by the diameter of the tubes and degree of nesting, compared with a surface area of about 3000 m2/g of activated carbons. Nevertheless, CNTs have higher capacitance than activated carbon electrodes, ''e.g.'', 102 F/g for MWNTs and 180 F/g for SWNTs. MWNTs have mesopores that allow for easy access of ions at the electrode–electrolyte interface. As the pore size approaches the size of the ion solvation shell, the solvent molecules are partially stripped, resulting in larger ionic packing density and increased faradaic storage capability. However, the considerable volume change during repeated intercalation and depletion decreases their mechanical stability. To this end, research to increase surface area, mechanical strength, electrical conductivity and chemical stability is ongoing.


Electrodes for pseudocapacitors

MnO2 and RuO2 are typical materials used as electrodes for pseudocapacitors, since they have the electrochemical signature of a capacitive electrode (linear dependence on current versus voltage curve) as well as exhibiting faradaic behavior. Additionally, the charge storage originates from electron-transfer mechanisms rather than accumulation of ions in the electrochemical double layer. Pseudocapacitors were created through faradaic redox reactions that occur within the active electrode materials. More research was focused on transition-metal oxides such as MnO2 since transition-metal oxides have a lower cost compared to noble metal oxides such as RuO2. Moreover, the charge storage mechanisms of transition-metal oxides are based predominantly on pseudocapacitance. Two mechanisms of MnO2 charge storage behavior were introduced. The first mechanism implies the intercalation of protons (H+) or alkali metal cations (C+) in the bulk of the material upon reduction followed by deintercalation upon oxidation. :MnO2 + H+(C+) +e MnOOH(C) The second mechanism is based on the surface adsorption of electrolyte cations on MnO2. :(MnO2)surface + C+ +e (MnO2 C+)surface Not every material that exhibits faradaic behavior can be used as an electrode for pseudocapacitors, such as Ni(OH)2 since it is a battery type electrode (non-linear dependence on current versus voltage curve).


= Metal oxides

= Brian Evans Conway's research described electrodes of transition metal oxides that exhibited high amounts of pseudocapacitance. Oxides of transition metals including
ruthenium Ruthenium is a chemical element with the Symbol (chemistry), symbol Ru and atomic number 44. It is a rare transition metal belonging to the platinum group of the periodic table. Like the other metals of the platinum group, ruthenium is inert to ...
(),
iridium Iridium is a chemical element with the symbol Ir and atomic number 77. A very hard, brittle, silvery-white transition metal of the platinum group, it is considered the second-densest naturally occurring metal (after osmium) with a density of ...
(),
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
(),
manganese Manganese is a chemical element with the symbol Mn and atomic number 25. It is a hard, brittle, silvery metal, often found in minerals in combination with iron. Manganese is a transition metal with a multifaceted array of industrial alloy use ...
() or sulfides such as
titanium sulfide Titanium(II) sulfide (TiS) is an inorganic chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by che ...
() alone or in combination generate strong faradaic electron–transferring reactions combined with low resistance. Ruthenium dioxide in combination with electrolyte provides specific capacitance of 720 F/g and a high specific energy of 26.7 Wh/kg (). Charge/discharge takes place over a window of about 1.2 V per electrode. This pseudocapacitance of about 720 F/g is roughly 100 times higher than for double-layer capacitance using activated carbon electrodes. These transition metal electrodes offer excellent reversibility, with several hundred-thousand cycles. However, ruthenium is expensive and the 2.4 V voltage window for this capacitor limits their applications to military and space applications. Das et al. reported highest capacitance value (1715 F/g) for ruthenium oxide based supercapacitor with electrodeposited ruthenium oxide onto porous single wall carbon nanotube film electrode. A high specific capacitance of 1715 F/g has been reported which closely approaches the predicted theoretical maximum capacitance of 2000 F/g. In 2014 a supercapacitor anchored on a
graphene foam Graphene foam is a solid, open-cell foam made of single-layer sheets of graphene. Supplement It is a candidate substrate for the electrode of lithium-ion battery, lithium-ion batteries. Synthesis The foam can be manufactured using vapor deposit ...
electrode delivered specific capacitance of 502.78 F/g and areal capacitance of 1.11 F/cm2) leading to a specific energy of 39.28 Wh/kg and specific power of 128.01 kW/kg over 8,000 cycles with constant performance. The device was a three-dimensional (3D) sub-5 nm hydrous ruthenium-anchored
graphene Graphene () is an allotrope of carbon consisting of a single layer of atoms arranged in a hexagonal lattice nanostructure.
and
carbon nanotube A scanning tunneling microscopy image of a single-walled carbon nanotube Rotating single-walled zigzag carbon nanotube A carbon nanotube (CNT) is a tube made of carbon with diameters typically measured in nanometers. ''Single-wall carbon na ...
(CNT) hybrid foam (RGM) architecture. The graphene foam was conformally covered with hybrid networks of nanoparticles and anchored CNTs. Less expensive oxides of iron, vanadium, nickel and cobalt have been tested in aqueous electrolytes, but none has been investigated as much as manganese dioxide (). However, none of these oxides are in commercial use.


= Conductive polymers

= Another approach uses electron-conducting polymers as pseudocapacitive material. Although mechanically weak,
conductive polymer Conductive polymers or, more precisely, intrinsically conducting polymers (ICPs) are organic polymers that conduct electricity. Such compounds may have metallic conductivity or can be semiconductors. The biggest advantage of conductive polymers ...
s have high
conductivity Conductivity may refer to: *Electrical conductivity, a measure of a material's ability to conduct an electric current **Conductivity (electrolytic), the electrical conductivity of an electrolyte in solution ** Ionic conductivity (solid state), ele ...
, resulting in a low ESR and a relatively high capacitance. Such conducting polymers include
polyaniline Polyaniline (PANI) is a conducting polymer and organic semiconductor of the semi-flexible rod polymer family. The compound has been of interest since the 1980s because of its electrical conductivity and mechanical properties. Polyaniline is one of ...
,
polythiophene Polythiophenes (PTs) are polymerized thiophenes, a sulfur heterocyclic compound, heterocycle. The parent PT is an insoluble colored solid with the formula (C4H2S)n. The rings are linked through the 2- and 5-positions. Poly(alkylthiophene)s hav ...
,
polypyrrole Polypyrrole (PPy) is an organic polymer obtained by oxidative polymerization of pyrrole. It is a solid with the formula H(C4H2NH)nH. It is an intrinsically conducting polymer, used in electronics, optical, biological and medical fields. History ...
and
polyacetylene Polyacetylene (IUPAC name: polyethyne) usually refers to an organic polymer with the repeating unit . The name refers to its conceptual construction from polymerization of acetylene to give a chain with repeating olefin groups. This compound ...
. Such electrodes also employ electrochemical doping or dedoping of the polymers with anions and cations. Electrodes made from or coated with conductive polymers have costs comparable to carbon electrodes. Conducting polymer electrodes generally suffer from limited cycling stability. However, polyacene electrodes provide up to 10,000 cycles, much better than batteries.


Electrodes for hybrid capacitors

All commercial hybrid supercapacitors are asymmetric. They combine an electrode with high amount of
pseudocapacitance Pseudocapacitance is the Electrochemistry, electrochemical storage of electricity in an Supercapacitor, electrochemical capacitor (Pseudocapacitor). This faradaic charge transfer originates by a very fast sequence of reversible Faradaic current, fa ...
with an electrode with a high amount of
double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
. In such systems the faradaic pseudocapacitance electrode with their higher capacitance provides high
specific energy Specific energy or massic energy is energy per unit mass. It is also sometimes called gravimetric energy density, which is not to be confused with energy density, which is defined as energy per unit volume. It is used to quantify, for example, sto ...
while the non-faradaic EDLC electrode enables high
specific power Power-to-weight ratio (PWR, also called specific power, or power-to-mass ratio) is a calculation commonly applied to engines and mobile power sources to enable the comparison of one unit or design to another. Power-to-weight ratio is a measuremen ...
. An advantage of the hybrid-type supercapacitors compared with symmetrical EDLC's is their higher specific capacitance value as well as their higher rated voltage and correspondingly their higher specific energy.


= Composite electrodes

= Composite electrodes for hybrid-type supercapacitors are constructed from carbon-based material with incorporated or deposited pseudocapacitive active materials like metal oxides and conducting polymers. most research for supercapacitors explores composite electrodes. CNTs give a backbone for a homogeneous distribution of metal oxide or electrically conducting polymers (ECPs), producing good pseudocapacitance and good double-layer capacitance. These electrodes achieve higher capacitances than either pure carbon or pure metal oxide or polymer-based electrodes. This is attributed to the accessibility of the nanotubes' tangled mat structure, which allows a uniform coating of pseudocapacitive materials and three-dimensional charge distribution. The process to anchor pseudocapacitve materials usually uses a hydrothermal process. However, a recent researcher, Li et al., from the University of Delaware found a facile and scalable approach to precipitate MnO2 on a SWNT film to make an organic-electrolyte based supercapacitor. Another way to enhance CNT electrodes is by doping with a pseudocapacitive dopant as in
lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
s. In this case the relatively small lithium atoms intercalate between the layers of carbon. The anode is made of lithium-doped carbon, which enables lower negative potential with a cathode made of activated carbon. This results in a larger voltage of 3.8-4 V that prevents electrolyte oxidation. As of 2007 they had achieved capacitance of 550 F/g. and reach a specific energy up to 14 Wh/kg ().


= Battery-type electrodes

= Rechargeable battery electrodes influenced the development of electrodes for new hybrid-type supercapacitor electrodes as for
lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
s. Together with a carbon EDLC electrode in an asymmetric construction offers this configuration higher specific energy than typical supercapacitors with higher specific power, longer cycle life and faster charging and recharging times than batteries.


= Asymmetric electrodes (pseudo/EDLC)

= Recently some asymmetric hybrid supercapacitors were developed in which the positive electrode were based on a real pseudocapacitive metal oxide electrode (not a composite electrode), and the negative electrode on an EDLC activated carbon electrode. Asymmetric supercapacitors (ASC) have shown a great potential candidate for high-performance supercapacitor due to their wide operating potential which can remarkably enhance the capacitive behavior. An advantage of this type of supercapacitors is their higher voltage and correspondingly their higher specific energy (up to 10-20 Wh/kg (36-72 kJ/kg)).And they also have good cycling stability. For example, researchers use a kind of novel skutterudite Ni–CoP3 nanosheets and use it as positive electrodes with activated carbon (AC) as negative electrodes to fabricate asymmetric supercapacitor (ASC). It exhibits high energy density of 89.6 Wh/kg at 796 W/kg and stability of 93% after 10000 cycles, which can be a great potential to be an excellent next-generation electrode candidate. Also, carbon nanofibers/poly(3,4-ethylenedioxythiophene)/manganese oxide (f-CNFs/PEDOT/MnO2) were used as positive electrodes and AC as negative electrodes. It has high specific energy of 49.4 Wh/kg and good cycling stability (81.06% after cycling 8000 times). Besides, many kinds of nanocomposite are being studied as electrodes, like NiCo2S4@NiO, MgCo2O4@MnO2 and so on. For example, Fe-SnO2@CeO2 nanocomposite used as electrode can provide a specific energy and specific power of 32.2 Wh/kg and 747 W/kg. The device exhibited the capacitance retention of 85.05 % over 5000 cycles of operation. As far as known no commercial offered supercapacitors with such kind of asymmetric electrodes are on the market.


Electrolytes

Electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
s consist of a
solvent A solvent (s) (from the Latin '' solvō'', "loosen, untie, solve") is a substance that dissolves a solute, resulting in a solution. A solvent is usually a liquid but can also be a solid, a gas, or a supercritical fluid. Water is a solvent for ...
and dissolved
chemicals A chemical substance is a form of matter having constant chemical composition and characteristic properties. Some references add that chemical substance cannot be separated into its constituent elements by physical separation methods, i.e., wit ...
that dissociate into positive
cation An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s and negative
anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s, making the electrolyte electrically conductive. The more ions the electrolyte contains, the better its
conductivity Conductivity may refer to: *Electrical conductivity, a measure of a material's ability to conduct an electric current **Conductivity (electrolytic), the electrical conductivity of an electrolyte in solution ** Ionic conductivity (solid state), ele ...
. In supercapacitors electrolytes are the electrically conductive connection between the two electrodes. Additionally, in supercapacitors the electrolyte provides the molecules for the separating monolayer in the Helmholtz double-layer and delivers the ions for pseudocapacitance. The electrolyte determines the capacitor's characteristics: its operating voltage, temperature range, ESR and capacitance. With the same activated carbon electrode an aqueous electrolyte achieves capacitance values of 160 F/g, while an organic electrolyte achieves only 100 F/g.P. Simon, A. Burke
Nanostructured Carbons: Double-Layer Capacitance and More
/ref> The electrolyte must be chemically inert and not chemically attack the other materials in the capacitor to ensure long time stable behavior of the capacitor's electrical parameters. The electrolyte's viscosity must be low enough to wet the porous, sponge-like structure of the electrodes. An ideal electrolyte does not exist, forcing a compromise between performance and other requirements.


Aqueous

Water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
is a relatively good solvent for
inorganic In chemistry, an inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds, that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as '' inorganic chemist ...
chemicals. Treated with
acid In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
s such as
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
(),
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
s such as
potassium hydroxide Potassium hydroxide is an inorganic compound with the formula K OH, and is commonly called caustic potash. Along with sodium hydroxide (NaOH), KOH is a prototypical strong base. It has many industrial and niche applications, most of which exp ...
(KOH), or
salts In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively cha ...
such as quaternary
phosphonium In polyatomic cations with the chemical formula (where R is a hydrogen or an alkyl, aryl, or halide group). These cations have tetrahedral structures. The salts are generally colorless or take the color of the anions. Types of phosphonium ...
salts,
sodium perchlorate Sodium perchlorate is the inorganic compound with the chemical formula Na ClO4. It is a white crystalline, hygroscopic solid that is highly soluble in water and in alcohol. It is usually encountered as the monohydrate. The compound is noteworth ...
(),
lithium perchlorate Lithium perchlorate is the inorganic compound with the formula LiClO4. This white or colourless crystalline salt is noteworthy for its high solubility in many solvents. It exists both in anhydrous form and as a trihydrate. Applications Inorga ...
() or lithium hexafluoride
arsenate The arsenate ion is . An arsenate (compound) is any compound that contains this ion. Arsenates are salts or esters of arsenic acid. The arsenic atom in arsenate has a valency of 5 and is also known as pentavalent arsenic or As(V). Arsenate res ...
(), water offers relatively high conductivity values of about 100 to 1000 m S/cm. Aqueous electrolytes have a dissociation voltage of 1.15 V per electrode (2.3 V capacitor voltage) and a relatively low
operating temperature An operating temperature is the allowable temperature range of the local ambient environment at which an electrical or mechanical device operates. The device will operate effectively within a specified temperature range which varies based on the de ...
range. They are used in supercapacitors with low specific energy and high specific power.


Organic

Electrolytes with organic solvents such as
acetonitrile Acetonitrile, often abbreviated MeCN (methyl cyanide), is the chemical compound with the formula and structure . This colourless liquid is the simplest organic nitrile (hydrogen cyanide is a simpler nitrile, but the cyanide anion is not clas ...
,
propylene carbonate Propylene carbonate (often abbreviated PC) is an organic compound with the formula C4H6O3. It is a cyclic carbonate ester derived from propylene glycol. This colorless and odorless liquid is useful as a polar, aprotic solvent. Propylene carbo ...
,
tetrahydrofuran Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is ma ...
,
diethyl carbonate Diethyl carbonate (sometimes abbreviated DEC) is an ester of carbonic acid and ethanol with the formula OC(OCH2CH3)2. At room temperature (25 °C) diethyl carbonate is a colorless liquid with a low flash point. Diethyl carbonate is used as ...
, γ-butyrolactone and solutions with quaternary
ammonium salt The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
s or alkyl ammonium salts such as tetraethylammonium
tetrafluoroborate Tetrafluoroborate is the anion . This tetrahedral species is isoelectronic with tetrafluoroberyllate (), tetrafluoromethane (CF4), and tetrafluoroammonium () and is valence isoelectronic with many stable and important species including the perchlo ...
() or triethyl (metyl) tetrafluoroborate () are more expensive than aqueous electrolytes, but they have a higher dissociation voltage of typically 1.35 V per electrode (2.7 V capacitor voltage), and a higher temperature range. The lower electrical conductivity of organic solvents (10 to 60 mS/cm) leads to a lower specific power, but since the specific energy increases with the square of the voltage, a higher specific energy.


Ionic

Ionic electrolytes consists of liquid salts that can be stable in a wider electrochemical window, enabling capacitor voltages above 3.5 V. Ionic electrolytes typically have an ionic conductivity of a few mS/cm, lower than aqueous or organic electrolytes.


Separators

Separators have to physically separate the two electrodes to prevent a short circuit by direct contact. It can be very thin (a few hundredths of a millimeter) and must be very porous to the conducting ions to minimize ESR. Furthermore, separators must be chemically inert to protect the electrolyte's stability and conductivity. Inexpensive components use open capacitor papers. More sophisticated designs use nonwoven porous polymeric films like
polyacrylonitrile Polyacrylonitrile (PAN), also known as polyvinyl cyanide and Creslan 61, is a synthetic, semicrystalline organic polymer resin, with the linear formula (C3H3N)n. Though it is thermoplastic, it does not melt under normal conditions. It degrades bef ...
or
Kapton Structure of poly-oxydiphenylene-pyromellitimide Kapton insulating pads for mounting electronic parts on a heat sink Kapton is a polyimide film used in flexible printed circuits (flexible electronics) and space blankets, which are used on spac ...
, woven glass fibers or porous woven ceramic fibres.


Collectors and housing

Current collectors connect the electrodes to the capacitor's terminals. The collector is either sprayed onto the electrode or is a metal foil. They must be able to distribute peak currents of up to 100 A. If the housing is made out of a metal (typically aluminum) the collectors should be made from the same material to avoid forming a corrosive
galvanic cell A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous Oxidation-Reduction reactions. A common apparatus ...
.


Electrical parameters


Capacitance

Capacitance values for commercial capacitors are specified as "rated capacitance CR". This is the value for which the capacitor has been designed. The value for an actual component must be within the limits given by the specified tolerance. Typical values are in the range of
farad The farad (symbol: F) is the unit of electrical capacitance, the ability of a body to store an electrical charge, in the International System of Units (SI). It is named after the English physicist Michael Faraday (1791–1867). In SI base unit ...
s (F), three to six
orders of magnitude An order of magnitude is an approximation of the logarithm of a value relative to some contextually understood reference value, usually 10, interpreted as the base of the logarithm and the representative of values of magnitude one. Logarithmic dis ...
larger than those of electrolytic capacitors. The capacitance value results from the energy W (expressed in
Joule The joule ( , ; symbol: J) is the unit of energy in the International System of Units (SI). It is equal to the amount of work done when a force of 1 newton displaces a mass through a distance of 1 metre in the direction of the force applied ...
) of a loaded capacitor loaded via a DC voltage VDC. :W=\frac\cdot C_\text \cdot V_\text^2 This value is also called the "DC capacitance".


Measurement

Conventional capacitors are normally measured with a small AC voltage (0.5 V) and a frequency of 100 Hz or 1 kHz depending on the capacitor type. The AC capacitance measurement offers fast results, important for industrial production lines. The capacitance value of a supercapacitor depends strongly on the measurement frequency, which is related to the porous electrode structure and the limited electrolyte's ion mobility. Even at a low frequency of 10 Hz, the measured capacitance value drops from 100 to 20 percent of the DC capacitance value. This extraordinary strong frequency dependence can be explained by the different distances the ions have to move in the electrode's pores. The area at the beginning of the pores can easily be accessed by the ions. The short distance is accompanied by low electrical resistance. The greater the distance the ions have to cover, the higher the resistance. This phenomenon can be described with a series circuit of cascaded RC (resistor/capacitor) elements with serial RC
time constant In physics and engineering, the time constant, usually denoted by the Greek letter (tau), is the parameter characterizing the response to a step input of a first-order, linear time-invariant (LTI) system.Concretely, a first-order LTI system is a sy ...
s. These result in delayed current flow, reducing the total electrode surface area that can be covered with ions if polarity changes – capacitance decreases with increasing AC frequency. Thus, the total capacitance is only achieved after longer measuring times. Out of the reason of the very strong frequency dependence of the capacitance this electrical parameter has to be measured with a special constant current charge and discharge measurement, defined in
IEC The International Electrotechnical Commission (IEC; in French: ''Commission électrotechnique internationale'') is an international standards organization that prepares and publishes international standards for all electrical, electronic and r ...
standards 62391-1 and -2. Measurement starts with charging the capacitor. The voltage has to be applied and after the constant current/constant voltage power supply has achieved the rated voltage, the capacitor has to be charged for 30 minutes. Next, the capacitor has to be discharged with a constant discharge current Idischarge. Then the time t1 and t2, for the voltage to drop from 80% (V1) to 40% (V2) of the rated voltage is measured. The capacitance value is calculated as: :C_\text = I_\text \cdot \frac The value of the discharge current is determined by the application. The IEC standard defines four classes: # Memory backup, discharge current in mA = 1 • C (F) # Energy storage, discharge current in mA = 0,4 • C (F) • V (V) # Power, discharge current in mA = 4 • C (F) • V (V) # Instantaneous power, discharge current in mA = 40 • C (F) • V (V) The measurement methods employed by individual manufacturers are mainly comparable to the standardized methods.Maxwell BOOSTCA
''Product Guide – Maxwell Technologies BOOSTCAP Ultracapacitors– Doc. No. 1014627.1''
Maxwell Technologies, Inc. 2009
The standardized measuring method is too time consuming for manufacturers to use during production for each individual component. For industrial produced capacitors the capacitance value is instead measured with a faster low frequency AC voltage and a correlation factor is used to compute the rated capacitance. This frequency dependence affects capacitor operation. Rapid charge and discharge cycles mean that neither the rated capacitance value nor specific energy are available. In this case the rated capacitance value is recalculated for each application condition.


Operating voltage

Supercapacitors are low voltage components. Safe operation requires that the voltage remain within specified limits. The rated voltage UR is the maximum DC voltage or peak pulse voltage that may be applied continuously and remain within the specified temperature range. Capacitors should never be subjected to voltages continuously in excess of the rated voltage. The rated voltage includes a safety margin against the electrolyte's
breakdown voltage The breakdown voltage of an insulator is the minimum voltage that causes a portion of an insulator to experience electrical breakdown and become electrically conductive. For diodes, the breakdown voltage is the minimum reverse voltage that mak ...
at which the electrolyte decomposes. The breakdown voltage decomposes the separating solvent molecules in the Helmholtz double-layer, e.g.
water Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
splits into
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
and
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
. The solvent molecules then cannot separate the electrical charges from each other. Higher voltages than rated voltage cause hydrogen gas formation or a short circuit. Standard supercapacitors with aqueous electrolyte normally are specified with a rated voltage of 2.1 to 2.3 V and capacitors with organic solvents with 2.5 to 2.7 V.
Lithium-ion capacitor A lithium-ion capacitor (LIC) is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercap ...
s with doped electrodes may reach a rated voltage of 3.8 to 4 V, but have a low voltage limit of about 2.2 V. Supercapacitors with ionic electrolytes can exceed an operating voltage of 3.5 V. Operating supercapacitors below the rated voltage improves the long-time behavior of the electrical parameters. Capacitance values and internal resistance during cycling are more stable and lifetime and charge/discharge cycles may be extended. Higher application voltages require connecting cells in series. Since each component has a slight difference in capacitance value and ESR, it is necessary to actively or passively balance them to stabilize the applied voltage. Passive balancing employs
resistor A resistor is a passive two-terminal electrical component that implements electrical resistance as a circuit element. In electronic circuits, resistors are used to reduce current flow, adjust signal levels, to divide voltages, bias active el ...
s in parallel with the supercapacitors. Active balancing may include electronic voltage management above a threshold that varies the current.


Internal resistance

Charging/discharging a supercapacitor is connected to the movement of charge carriers (ions) in the electrolyte across the separator to the electrodes and into their porous structure. Losses occur during this movement that can be measured as the internal DC resistance. With the electrical model of cascaded, series-connected RC (resistor/capacitor) elements in the electrode pores, the internal resistance increases with the increasing penetration depth of the charge carriers into the pores. The internal DC resistance is time dependent and increases during charge/discharge. In applications often only the switch-on and switch-off range is interesting. The internal resistance Ri can be calculated from the voltage drop ΔV2 at the time of discharge, starting with a constant discharge current Idischarge. It is obtained from the intersection of the auxiliary line extended from the straight part and the time base at the time of discharge start (see picture right). Resistance can be calculated by: : R_\text= \frac The discharge current Idischarge for the measurement of internal resistance can be taken from the classification according to IEC 62391-1. This internal DC resistance Ri should not be confused with the internal AC resistance called
equivalent series resistance Practical capacitors and inductors as used in electric circuits are not ideal components with only capacitance or inductance. However, they can be treated, to a very good degree of approximation, as being ideal capacitors and inductors in series ...
(ESR) normally specified for capacitors. It is measured at 1 kHz. ESR is much smaller than DC resistance. ESR is not relevant for calculating supercapacitor inrush currents or other peak currents. Ri determines several supercapacitor properties. It limits the charge and discharge peak currents as well as charge/discharge times. Ri and the capacitance C results in the
time constant In physics and engineering, the time constant, usually denoted by the Greek letter (tau), is the parameter characterizing the response to a step input of a first-order, linear time-invariant (LTI) system.Concretely, a first-order LTI system is a sy ...
\tau :\tau = R_\text \cdot C This time constant determines the charge/discharge time. A 100 F capacitor with an internal resistance of 30 mΩ for example, has a time constant of 0.03 • 100 = 3 s. After 3 seconds charging with a current limited only by internal resistance, the capacitor has 63.2% of full charge (or is discharged to 36.8% of full charge). Standard capacitors with constant internal resistance fully charge during about 5 τ. Since internal resistance increases with charge/discharge, actual times cannot be calculated with this formula. Thus, charge/discharge time depends on specific individual construction details.


Current load and cycle stability

Because supercapacitors operate without forming chemical bonds, current loads, including charge, discharge and peak currents are not limited by reaction constraints. Current load and cycle stability can be much higher than for rechargeable batteries. Current loads are limited only by internal resistance, which may be substantially lower than for batteries. Internal resistance "Ri" and charge/discharge currents or peak currents "I" generate internal heat losses "Ploss" according to: :P_\text = R_\text \cdot I^2 This heat must be released and distributed to the ambient environment to maintain operating temperatures below the specified maximum temperature. Heat generally defines capacitor lifetime due to electrolyte diffusion. The heat generation coming from current loads should be smaller than 5 to 10  K at maximum ambient temperature (which has only minor influence on expected lifetime). For that reason the specified charge and discharge currents for frequent cycling are determined by internal resistance. The specified cycle parameters under maximal conditions include charge and discharge current, pulse duration and frequency. They are specified for a defined temperature range and over the full voltage range for a defined lifetime. They can differ enormously depending on the combination of electrode porosity, pore size and electrolyte. Generally a lower current load increases capacitor life and increases the number of cycles. This can be achieved either by a lower voltage range or slower charging and discharging. Supercapacitors (except those with polymer electrodes) can potentially support more than one million charge/discharge cycles without substantial capacity drops or internal resistance increases. Beneath the higher current load is this the second great advantage of supercapacitors over batteries. The stability results from the dual electrostatic and electrochemical storage principles. The specified charge and discharge currents can be significantly exceeded by lowering the frequency or by single pulses. Heat generated by a single pulse may be spread over the time until the next pulse occurs to ensure a relatively small average heat increase. Such a "peak power current" for power applications for supercapacitors of more than 1000 F can provide a maximum peak current of about 1000 A. Such high currents generate high thermal stress and high electromagnetic forces that can damage the electrode-collector connection requiring robust design and construction of the capacitors.


Device capacitance and resistance dependence on operating voltage and temperature

Device parameters such as capacitance initial resistance and steady state resistance are not constant, but are variable and dependent on the device's operating voltage. Device capacitance will have a measurable increase as the operating voltage increases. For example: a 100F device can be seen to vary 26% from its maximum capacitance over its entire operational voltage range. Similar dependence on operating voltage is seen in steady state resistance (Rss) and initial resistance (Ri). Device properties can also be seen to be dependent on device temperature. As the temperature of the device changes either through operation of varying ambient temperature, the internal properties such as capacitance and resistance will vary as well. Device capacitance is seen to increase as the operating temperature increases.


Energy capacity

Supercapacitors occupy the gap between high power/low energy
electrolytic capacitor An electrolytic capacitor is a polarized capacitor whose anode or positive plate is made of a metal that forms an insulating oxide layer through anodization. This oxide layer acts as the dielectric of the capacitor. A solid, liquid, or gel el ...
s and low power/high energy rechargeable batteries. The energy Wmax (expressed in
Joule The joule ( , ; symbol: J) is the unit of energy in the International System of Units (SI). It is equal to the amount of work done when a force of 1 newton displaces a mass through a distance of 1 metre in the direction of the force applied ...
) that can be stored in a capacitor is given by the formula : W_\text=\frac\cdot C_\text \cdot V_\text^2 This formula describes the amount of energy stored and is often used to describe new research successes. However, only part of the stored energy is available to applications, because the voltage drop and the time constant over the internal resistance mean that some of the stored charge is inaccessible. The effective realized amount of energy Weff is reduced by the used voltage difference between Vmax and Vmin and can be represented as: : W_\text=\frac\ C \cdot\ ( V_\text^2 - V_\text^2 ) This formula also represents the energy asymmetric voltage components such as lithium ion capacitors.


Specific energy and specific power

The amount of energy that can be stored in a capacitor ''per mass'' of that capacitor is called its
specific energy Specific energy or massic energy is energy per unit mass. It is also sometimes called gravimetric energy density, which is not to be confused with energy density, which is defined as energy per unit volume. It is used to quantify, for example, sto ...
. Specific energy is measured gravimetrically (per unit of
mass Mass is an intrinsic property of a body. It was traditionally believed to be related to the quantity of matter in a physical body, until the discovery of the atom and particle physics. It was found that different atoms and different elementar ...
) in watt-hours per kilogram (Wh/kg). The amount of energy can be stored in a capacitor ''per volume'' of that capacitor is called its energy density (also called volumetric specific energy in some literature). Energy density is measured
volume Volume is a measure of occupied three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch). The de ...
trically (per unit of volume) in watt-hours per
litre The litre (international spelling) or liter (American English spelling) (SI symbols L and l, other symbol used: ℓ) is a metric unit of volume. It is equal to 1 cubic decimetre (dm3), 1000 cubic centimetres (cm3) or 0.001 cubic metre (m3). ...
(Wh/L). Units of liters and dm3 can be used interchangeably. commercial energy density varies widely, but in general range from around 5 to . In comparison, petrol fuel has an
energy density In physics, energy density is the amount of energy stored in a given system or region of space per unit volume. It is sometimes confused with energy per unit mass which is properly called specific energy or . Often only the ''useful'' or extract ...
of 32.4 MJ/L or . Commercial specific energies range from around 0.5 to . For comparison, an aluminum electrolytic capacitor stores typically 0.01 to , while a conventional lead-acid battery stores typically 30 to and modern
lithium-ion batteries A lithium-ion or Li-ion battery is a type of rechargeable battery which uses the reversible reduction of lithium ions to store energy. It is the predominant battery type used in portable consumer electronics and electric vehicles. It also se ...
100 to . Supercapacitors can therefore store 10 to 100 times more energy than electrolytic capacitors, but only one tenth as much as batteries. For reference, petrol fuel has a specific energy of 44.4 MJ/kg or . Although the specific energy of supercapacitors is defavorably compared with batteries, capacitors have the important advantage of the
specific power Power-to-weight ratio (PWR, also called specific power, or power-to-mass ratio) is a calculation commonly applied to engines and mobile power sources to enable the comparison of one unit or design to another. Power-to-weight ratio is a measuremen ...
. Specific power describes the speed at which energy can be delivered to the load (or, in charging the device, absorbed from the generator). The maximum power Pmax specifies the power of a theoretical rectangular single maximum current peak of a given voltage. In real circuits the current peak is not rectangular and the voltage is smaller, caused by the voltage drop, so IEC 62391–2 established a more realistic effective power Peff for supercapacitors for power applications, which is half the maximum and given by the following formulas : : P_\text=\frac\cdot\frac , : P_\text=\frac\cdot\frac with V = voltage applied and Ri, the internal DC resistance of the capacitor. Just like specific energy, specific power is measured either gravimetrically in kilowatts per kilogram (kW/kg, specific power) or volumetrically in kilowatts per litre (kW/L, power density). Supercapacitor specific power is typically 10 to 100 times greater than for batteries and can reach values up to 15 kW/kg. Ragone charts relate energy to power and are a valuable tool for characterizing and visualizing energy storage components. With such a diagram, the position of specific power and specific energy of different storage technologies is easily to compare, see diagram.


Lifetime

Since supercapacitors do not rely on chemical changes in the electrodes (except for those with polymer electrodes), lifetimes depend mostly on the rate of evaporation of the liquid electrolyte. This evaporation is generally a function of temperature, current load, current cycle frequency and voltage. Current load and cycle frequency generate internal heat, so that the evaporation-determining temperature is the sum of ambient and internal heat. This temperature is measurable as core temperature in the center of a capacitor body. The higher the core temperature the faster the evaporation and the shorter the lifetime. Evaporation generally results in decreasing capacitance and increasing internal resistance. According to IEC/EN 62391-2 capacitance reductions of over 30% or internal resistance exceeding four times its data sheet specifications are considered "wear-out failures", implying that the component has reached end-of-life. The capacitors are operable, but with reduced capabilities. Whether the aberration of the parameters have any influence on the proper functionality or not depends on the application of the capacitors. Such large changes of electrical parameters specified in IEC/EN 62391-2 are usually unacceptable for high current load applications. Components that support high current loads use much smaller limits, ''e.g.'', 20% loss of capacitance or double the internal resistance.Maxwell Application Not
''Application Note - Energy Storage Modules Life Duration Estimation.''
Maxwell Technologies, Inc. 2007
The narrower definition is important for such applications, since heat increases linearly with increasing internal resistance and the maximum temperature should not be exceeded. Temperatures higher than specified can destroy the capacitor. The real application lifetime of supercapacitors, also called "
service life A product's service life is its period of use in service. Several related terms describe more precisely a product's life, from the point of manufacture, storage, and distribution, and eventual use. Service life has been defined as "a product li ...
", "life expectancy" or "load life", can reach 10 to 15 years or more at room temperature. Such long periods cannot be tested by manufacturers. Hence, they specify the expected capacitor lifetime at the maximum temperature and voltage conditions. The results are specified in datasheets using the notation "tested time (hours)/max. temperature (°C)", such as "5000 h/65 °C". With this value and expressions derived from historical data, lifetimes can be estimated for lower temperature conditions. Datasheet lifetime specification is tested by the manufactures using an
accelerated aging Accelerated aging is testing that uses aggravated conditions of heat, humidity, oxygen, sunlight, vibration, etc. to speed up the normal aging processes of items. It is used to help determine the long-term effects of expected levels of stress wit ...
test called "endurance test" with maximum temperature and voltage over a specified time. For a "zero defect" product policy during this test no wear out or total failure may occur. The lifetime specification from datasheets can be used to estimate the expected lifetime for a given design. The "10-degrees-rule" used for electrolytic capacitors with non-solid electrolyte is used in those estimations and can be used for supercapacitors. This rule employs the
Arrhenius equation In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates. The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 18 ...
, a simple formula for the temperature dependence of reaction rates. For every 10 °C reduction in operating temperature, the estimated life doubles. :L_x =L_0\cdot 2^\frac With *Lx = estimated lifetime *L0 = specified lifetime *T0 = upper specified capacitor temperature *Tx = actual operating temperature of the capacitor cell Calculated with this formula, capacitors specified with 5000 h at 65 °C, have an estimated lifetime of 20,000 h at 45 °C. Lifetimes are also dependent on the operating voltage, because the development of gas in the liquid electrolyte depends on the voltage. The lower the voltage the smaller the gas development and the longer the lifetime. No general formula relates voltage to lifetime. The voltage dependent curves shown from the picture are an empirical result from one manufacturer. Life expectancy for power applications may be also limited by current load or number of cycles. This limitation has to be specified by the relevant manufacturer and is strongly type dependent.


Self-discharge

Storing electrical energy in the double-layer separates the charge carriers within the pores by distances in the range of molecules. Over this short distance irregularities can occur, leading to a small exchange of charge carriers and gradual discharge. This self-discharge is called
leakage current In electronics, leakage is the gradual transfer of electrical energy across a boundary normally viewed as insulating, such as the spontaneous discharge of a charged capacitor, magnetic coupling of a transformer with other components, or flow of cu ...
. Leakage depends on capacitance, voltage, temperature and the chemical stability of the electrode/electrolyte combination. At room temperature leakage is so low that it is specified as time to self-discharge. Supercapacitor self-discharge time is specified in hours, days or weeks. As an example, a 5.5 V/F Panasonic "Goldcapacitor" specifies a voltage drop at 20 °C from 5.5 V to 3 V in 600 hours (25 days or 3.6 weeks) for a double cell capacitor.


Post charge voltage relaxation

It has been noticed that after the EDLC experiences a charge or discharge, the voltage will drift over time, relaxing toward its previous voltage level. The observed relaxation can occur over several hours and is likely due to long diffusion time constants of the porous electrodes within the EDLC.


Polarity

Since the positive and negative electrodes (or simply positrode and negatrode, respectively) of symmetric supercapacitors consist of the same material, theoretically supercapacitors have no true
polarity Polarity may refer to: Science *Electrical polarity, direction of electrical current *Polarity (mutual inductance), the relationship between components such as transformer windings * Polarity (projective geometry), in mathematics, a duality of ord ...
and catastrophic failure does not normally occur. However reverse-charging a supercapacitor lowers its capacity, so it is recommended practice to maintain the polarity resulting from the formation of the electrodes during production. Asymmetric supercapacitors are inherently polar. Pseudocapacitor and hybrid supercapacitors which have electrochemical charge properties may not be operated with reverse polarity, precluding their use in AC operation. However, this limitation does not apply to EDLC supercapacitors A bar in the insulating sleeve identifies the negative terminal in a polarized component. In some literature, the terms "anode" and "cathode" are used in place of negative electrode and positive electrode. Using anode and cathode to describe the electrodes in supercapacitors (and also rechargeable batteries including lithium ion batteries) can lead to confusion, because the polarity changes depending on whether a component is considered as a generator or as a consumer of current. In electrochemistry, cathode and anode are related to reduction and oxidation reactions, respectively. However, in supercapacitors based on electric double layer capacitance, there is no oxidation nor reduction reactions on any of the two electrodes. Therefore, the concepts of cathode and anode do not apply.


Comparison of selected commercial supercapacitors

The range of electrodes and electrolytes available yields a variety of components suitable for diverse applications. The development of low-ohmic electrolyte systems, in combination with electrodes with high pseudocapacitance, enable many more technical solutions. The following table shows differences among capacitors of various manufacturers in capacitance range, cell voltage, internal resistance (ESR, DC or AC value) and volumetric and gravimetric specific energy. In the table, ESR refers to the component with the largest capacitance value of the respective manufacturer. Roughly, they divide supercapacitors into two groups. The first group offers greater ESR values of about 20 milliohms and relatively small capacitance of 0.1 to 470 F. These are "double-layer capacitors" for memory back-up or similar applications. The second group offers 100 to 10,000 F with a significantly lower ESR value under 1 milliohm. These components are suitable for power applications. A correlation of some supercapacitor series of different manufacturers to the various construction features is provided in Pandolfo and Hollenkamp. In commercial double-layer capacitors, or, more specifically, EDLCs in which energy storage is predominantly achieved by double-layer capacitance, energy is stored by forming an electrical double layer of electrolyte ions on the surface of conductive electrodes. Since EDLCs are not limited by the electrochemical charge transfer kinetics of batteries, they can charge and discharge at a much higher rate, with lifetimes of more than 1 million cycles. The EDLC energy density is determined by operating voltage and the specific capacitance (farad/gram or farad/cm3) of the electrode/electrolyte system. The specific capacitance is related to the Specific Surface Area (SSA) accessible by the electrolyte, its interfacial double-layer capacitance, and the electrode material density. Commercial EDLCs are based on two symmetric electrodes impregnated with electrolytes comprising tetraethylammonium tetrafluoroborate salts in organic solvents. Current EDLCs containing organic electrolytes operate at 2.7 V and reach energy densities around 5-8 Wh/kg and 7 to 10 Wh/L. The specific capacitance is related to the specific surface area (SSA) accessible by the electrolyte, its interfacial double-layer capacitance, and the electrode material density. Graphene-based platelets with mesoporous spacer material is a promising structure for increasing the SSA of the electrolyte.


Standards

Supercapacitors vary sufficiently that they are rarely interchangeable, especially those with higher specific energy. Applications range from low to high peak currents, requiring standardized test protocols.P. Van den Bossche et al.:
The Cell versus the System: Standardization challenges for electricity storage devices
' EVS24 International Battery, Hybrid and Fuel Cell Electric Vehicle Symposium, Stavanger/Norway 2009
Test specifications and parameter requirements are specified in the generic specification *
IEC The International Electrotechnical Commission (IEC; in French: ''Commission électrotechnique internationale'') is an international standards organization that prepares and publishes international standards for all electrical, electronic and r ...
/ EN 62391–1, ''Fixed electric double layer capacitors for use in electronic equipment''. The standard defines four application classes, according to discharge current levels: # Memory backup # Energy storage, mainly used for driving motors require a short time operation, # Power, higher power demand for a long time operation, # Instantaneous power, for applications that requires relatively high current units or peak currents ranging up to several hundreds of amperes even with a short operating time Three further standards describe special applications: * IEC 62391–2, ''Fixed electric double-layer capacitors for use in electronic equipment - Blank detail specification - Electric double-layer capacitors for power application'' * IEC 62576, ''Electric double-layer capacitors for use in hybrid electric vehicles. Test methods for electrical characteristics'' * BS/EN 61881-3, ''Railway applications. Rolling stock equipment. Capacitors for power electronics. Electric double-layer capacitors''


Applications

Supercapacitors do not support alternating current (AC) applications. Supercapacitors have advantages in applications where a large amount of power is needed for a relatively short time, where a very high number of charge/discharge cycles or a longer lifetime is required. Typical applications range from milliamp currents or milliwatts of power for up to a few minutes to several amps current or several hundred kilowatts power for much shorter periods. The time t a supercapacitor can deliver a constant current I can be calculated as: : t=\frac as the capacitor voltage decreases from Ucharge down to Umin. If the application needs a constant power P for a certain time t this can be calculated as: : t=\frac\cdot C\cdot(U_\text^2-U_\text^2). wherein also the capacitor voltage decreases from Ucharge down to Umin.


General


Consumer electronics

In applications with fluctuating loads, such as
laptop A laptop, laptop computer, or notebook computer is a small, portable personal computer (PC) with a screen and alphanumeric keyboard. Laptops typically have a clam shell form factor with the screen mounted on the inside of the upper li ...
computers, PDAs,
GPS The Global Positioning System (GPS), originally Navstar GPS, is a Radionavigation-satellite service, satellite-based radionavigation system owned by the United States government and operated by the United States Space Force. It is one of t ...
,
portable media player A portable media player (PMP) (also including the related digital audio player (DAP)) is a portable consumer electronics device capable of storing and playing digital media such as audio, images, and video files. The data is typically stored o ...
s, hand-held devices, and
photovoltaic system A photovoltaic system, also PV system or solar power system, is an electric power system designed to supply usable solar power by means of photovoltaics. It consists of an arrangement of several components, including solar panels to absorb and co ...
s, supercapacitors can stabilize the power supply. Supercapacitors deliver power for photographic flashes in
digital camera A digital camera is a camera that captures photographs in digital memory. Most cameras produced today are digital, largely replacing those that capture images on photographic film. Digital cameras are now widely incorporated into mobile device ...
s and for
LED A light-emitting diode (LED) is a semiconductor Electronics, device that Light#Light sources, emits light when Electric current, current flows through it. Electrons in the semiconductor recombine with electron holes, releasing energy i ...
flashlights that can be charged in much shorter periods of time, ''e.g.'', 90 seconds. Some portable speakers are powered by supercapacitors.


Tools

A cordless electric screwdriver with supercapacitors for energy storage has about half the run time of a comparable battery model, but can be fully charged in 90 seconds. It retains 85% of its charge after three months left idle.


Grid power buffer

Numerous non-linear loads, such as EV chargers, HEVs, air conditioning systems, and advanced power conversion systems cause current fluctuations and harmonics. These current differences create unwanted voltage fluctuations and therefore power oscillations on the grid.M. Farhadi and O. Mohammed
Real-time operation and harmonic analysis of isolated and non-isolated hybrid DC microgrid
IEEE Trans. Ind. Appl., vol.50, no.4, pp.2900–2909, Jul./Aug. 2014.
Power oscillations not only reduce the efficiency of the grid, but can cause voltage drops in the common coupling bus, and considerable frequency fluctuations throughout the entire system. To overcome this problem, supercapacitors can be implemented as an interface between the load and the grid to act as a buffer between the grid and the high pulse power drawn from the charging station.


Low-power equipment power buffer

Supercapacitors provide backup or emergency shutdown power to low-power equipment such as
RAM Ram, ram, or RAM may refer to: Animals * A male sheep * Ram cichlid, a freshwater tropical fish People * Ram (given name) * Ram (surname) * Ram (director) (Ramsubramaniam), an Indian Tamil film director * RAM (musician) (born 1974), Dutch * ...
, SRAM, micro-controllers and
PC Card In computing, PC Card is a configuration for computer parallel communication peripheral interface, designed for laptop computers. Originally introduced as PCMCIA, the PC Card standard as well as its successors like CardBus were defined and devel ...
s. They are the sole power source for low energy applications such as automated meter reading (AMR)R. Gallay, Garmanage
Technologies and applications of Supercapacitors
, University of Mondragon, 22 June 2012
equipment or for event notification in industrial electronics. Supercapacitors buffer power to and from
rechargeable batteries A rechargeable battery, storage battery, or secondary cell (formally a type of energy accumulator), is a type of electrical battery which can be charged, discharged into a load, and recharged many times, as opposed to a disposable or prima ...
, mitigating the effects of short power interruptions and high current peaks. Batteries kick in only during extended interruptions, ''e.g.'', if the
mains power Mains electricity or utility power, power grid, domestic power, and wall power, or in some parts of Canada as hydro, is a general-purpose alternating-current (AC) electric power supply. It is the form of electrical power that is delivered to ...
or a
fuel cell A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requ ...
fails, which lengthens battery life.
Uninterruptible power supplies An uninterruptible power supply or uninterruptible power source (UPS) is an electrical apparatus that provides emergency power to a load when the input power source or mains power fails. A UPS differs from an auxiliary or emergency power system ...
(UPS) may be powered by supercapacitors, which can replace much larger banks of electrolytic capacitors. This combination reduces the cost per cycle, saves on replacement and maintenance costs, enables the battery to be downsized and extends battery life. Supercapacitors provide backup power for
actuator An actuator is a component of a machine that is responsible for moving and controlling a mechanism or system, for example by opening a valve. In simple terms, it is a "mover". An actuator requires a control device (controlled by control signal) a ...
s in
wind turbine A wind turbine is a device that converts the kinetic energy of wind into electrical energy. Hundreds of thousands of large turbines, in installations known as wind farms, now generate over 650 gigawatts of power, with 60 GW added each year. ...
pitch systems, so that blade pitch can be adjusted even if the main supply fails.


Voltage stabilizer

Supercapacitors can stabilize voltage fluctuations for powerlines by acting as dampers. Wind and
photovoltaic system A photovoltaic system, also PV system or solar power system, is an electric power system designed to supply usable solar power by means of photovoltaics. It consists of an arrangement of several components, including solar panels to absorb and co ...
s exhibit fluctuating supply evoked by gusting or clouds that supercapacitors can buffer within milliseconds.


Micro grids

Micro grids are usually powered by clean and renewable energy. Most of this energy generation, however, is not constant throughout the day and does not usually match demand. Supercapacitors can be used for micro grid storage to instantaneously inject power when the demand is high and the production dips momentarily, and to store energy in the reverse conditions. They are useful in this scenario, because micro grids are increasingly producing power in DC, and capacitors can be utilized in both DC and AC applications. Supercapacitors work best in conjunction with chemical batteries. They provide an immediate voltage buffer to compensate for quick changing power loads due to their high charge and discharge rate through an active control system. Once the voltage is buffered, it is put through an inverter to supply AC power to the grid. It is important to note that supercapacitors cannot provide frequency correction in this form directly in the AC grid.


Energy harvesting

Supercapacitors are suitable temporary energy storage devices for
energy harvesting Energy harvesting (EH, also known as power harvesting or energy scavenging or ambient power) is the process by which energy is derived from external sources (e.g., solar power, thermal energy, wind energy, salinity gradients, and kinetic energ ...
systems. In energy harvesting systems, the energy is collected from the ambient or renewable sources, ''e.g.'', mechanical movement, light or
electromagnetic fields An electromagnetic field (also EM field or EMF) is a classical (i.e. non-quantum) field produced by (stationary or moving) electric charges. It is the field described by classical electrodynamics (a classical field theory) and is the classical co ...
, and converted to electrical energy in an
energy storage Energy storage is the capture of energy produced at one time for use at a later time to reduce imbalances between energy demand and energy production. A device that stores energy is generally called an accumulator or battery. Energy comes in ...
device. For example, it was demonstrated that energy collected from RF (
radio frequency Radio frequency (RF) is the oscillation rate of an alternating electric current or voltage or of a magnetic, electric or electromagnetic field or mechanical system in the frequency range from around to around . This is roughly between the upp ...
) fields (using an RF antenna as an appropriate
rectifier A rectifier is an electrical device that converts alternating current (AC), which periodically reverses direction, to direct current (DC), which flows in only one direction. The reverse operation (converting DC to AC) is performed by an Power ...
circuit) can be stored to a printed supercapacitor. The harvested energy was then used to power an application-specific integrated circuit ( ASIC) for over 10 hours.


Incorporation into batteries

The
UltraBattery UltraBattery (commonly sold as Lead-Carbon batteries) is a hybrid energy storage device invented by Australia's Commonwealth Scientific and Industrial Research Organisation (CSIRO). UltraBattery combines ultracapacitor technology with lead-acid ...
is a hybrid rechargeable lead-acid battery and a supercapacitor. Its cell construction contains a standard lead-acid battery positive electrode, standard sulphuric acid electrolyte and a specially prepared negative carbon-based electrode that store electrical energy with
double-layer capacitance Double-layer capacitance is the important characteristic of the electrical double layer which appears, for example, at the interface between a conductive electrode and an adjacent liquid electrolyte. At this boundary two layers of charge with oppo ...
. The presence of the supercapacitor electrode alters the chemistry of the battery and affords it significant protection from sulfation in high rate partial state of charge use, which is the typical failure mode of valve regulated lead-acid cells used this way. The resulting cell performs with characteristics beyond either a lead-acid cell or a supercapacitor, with charge and discharge rates, cycle life, efficiency and performance all enhanced.


Medical

Supercapacitors are used in
defibrillator Defibrillation is a treatment for life-threatening cardiac arrhythmias, specifically ventricular fibrillation (V-Fib) and non-perfusing ventricular tachycardia (V-Tach). A defibrillator delivers a dose of electric current (often called a ''coun ...
s where they can deliver 500
joule The joule ( , ; symbol: J) is the unit of energy in the International System of Units (SI). It is equal to the amount of work done when a force of 1 newton displaces a mass through a distance of 1 metre in the direction of the force applied ...
s to shock the heart back into
sinus rhythm A sinus rhythm is any cardiac rhythm in which depolarisation of the cardiac muscle begins at the sinus node. It is characterised by the presence of correctly oriented P waves on the electrocardiogram (ECG). Sinus rhythm is necessary, but not su ...
.


Transport


Aviation

In 2005, aerospace systems and controls company Diehl Luftfahrt Elektronik GmbH chose supercapacitors to power emergency actuators for doors and
evacuation slide An evacuation slide is an inflatable slide used to evacuate an aircraft quickly. An escape slide is required on all commercial (passenger carrying) aircraft where the door sill height is such that, in the event of an evacuation, passengers wou ...
s used in
airliner An airliner is a type of aircraft for transporting passengers and air cargo. Such aircraft are most often operated by airlines. Although the definition of an airliner can vary from country to country, an airliner is typically defined as an ...
s, including the
Airbus 380 The Airbus A380 is a large wide-body airliner that was developed and produced by Airbus. It is the world's largest passenger airliner and only full-length double-deck jet airliner. Airbus studies started in 1988, and the project was annou ...
.


Military

Supercapacitors' low internal resistance supports applications that require short-term high currents. Among the earliest uses were motor startup (cold engine starts, particularly with diesels) for large engines in tanks and submarines. Supercapacitors buffer the battery, handling short current peaks, reducing cycling and extending battery life. Further military applications that require high specific power are phased array radar antennae, laser power supplies, military radio communications, avionics displays and instrumentation, backup power for airbag deployment and GPS-guided missiles and projectiles.


Automotive

Toyota's Yaris Hybrid-R concept car uses a supercapacitor to provide bursts of power.
PSA Peugeot Citroën The PSA Group (), legally known as Peugeot S.A. (Peugeot Société Anonyme, trading as Groupe PSA; formerly known as PSA Peugeot Citroën from 1991 to 2016) was a French multinational automotive manufacturing company which produced automobiles ...
has started using supercapacitors as part of its stop-start fuel-saving system, which permits faster initial acceleration. Mazda's i-ELOOP system stores energy in a supercapacitor during deceleration and uses it to power on-board electrical systems while the engine is stopped by the stop-start system.


Bus/tram

Maxwell Technologies, an American supercapacitor-maker, claimed that more than 20,000 hybrid buses use the devices to increase acceleration, particularly in China. Guangzhou, In 2014 China began using
trams A tram (called a streetcar or trolley in North America) is a rail vehicle that travels on tramway tracks on public urban streets; some include segments on segregated right-of-way. The tramlines or networks operated as public transport are ...
powered with supercapacitors that are recharged in 30 seconds by a device positioned between the rails, storing power to run the tram for up to 4 km — more than enough to reach the next stop, where the cycle can be repeated. CAF also offers supercapacitors on their
Urbos 3 The CAF Urbos is a family of trams, streetcars, and light rail vehicles built by CAF. The Basque manufacturer CAF previously manufactured locomotives, passenger cars, regional, and underground trains. In 1993, CAF started building trams for Metr ...
trams in the form of their ACR system.


Energy recovery

A primary challenge of all transport is reducing energy consumption and reducing emissions. Recovery of braking energy (recuperation or
regenerative braking Regenerative braking is an energy recovery mechanism that slows down a moving vehicle or object by converting its kinetic energy into a form that can be either used immediately or stored until needed. In this mechanism, the electric traction mo ...
) helps with both. This requires components that can quickly store and release energy over long times with a high cycle rate. Supercapacitors fulfill these requirements and are therefore used in various applications in transportation.


Railway

Supercapacitors can be used to supplement batteries in starter systems in
diesel Diesel may refer to: * Diesel engine, an internal combustion engine where ignition is caused by compression * Diesel fuel, a liquid fuel used in diesel engines * Diesel locomotive, a railway locomotive in which the prime mover is a diesel engin ...
railroad
locomotives A locomotive or engine is a rail transport vehicle that provides the motive power for a train. If a locomotive is capable of carrying a payload, it is usually rather referred to as a multiple unit, motor coach, railcar or power car; the u ...
with diesel-electric transmission. The capacitors capture the braking energy of a full stop and deliver the peak current for starting the diesel engine and acceleration of the train and ensures the stabilization of line voltage. Depending on the driving mode up to 30% energy saving is possible by recovery of braking energy. Low maintenance and environmentally friendly materials encouraged the choice of supercapacitors.


Cranes, forklifts and tractors

Mobile hybrid
Diesel Diesel may refer to: * Diesel engine, an internal combustion engine where ignition is caused by compression * Diesel fuel, a liquid fuel used in diesel engines * Diesel locomotive, a railway locomotive in which the prime mover is a diesel engin ...
-electric
rubber tyred gantry crane A rubber tyred gantry crane / RTG (crane), or sometimes transtainer, is a wheeled mobile gantry crane operated to ground or stack intermodal containers. Inbound containers are stored for future pickup by drayage trucks, and outbound are stored f ...
s move and stack containers within a terminal. Lifting the boxes requires large amounts of energy. Some of the energy could be recaptured while lowering the load, resulting in improved efficiency. A triple hybrid
forklift truck A forklift (also called lift truck, jitney, hi-lo, fork truck, fork hoist, and forklift truck) is a powered industrial truck used to lift and move materials over short distances. The forklift was developed in the early 20th century by various c ...
uses fuel cells and batteries as primary energy storage and supercapacitors to buffer power peaks by storing braking energy. They provide the fork lift with peak power over 30 kW. The triple-hybrid system offers over 50% energy savings compared with Diesel or fuel-cell systems. Supercapacitor-powered terminal tractors transport containers to warehouses. They provide an economical, quiet and pollution-free alternative to Diesel terminal tractors.


Light-rails and trams

Supercapacitors make it possible not only to reduce energy, but to replace
overhead lines An overhead line or overhead wire is an electrical cable that is used to transmit electrical energy to electric locomotives, trolleybuses or trams. It is known variously as: * Overhead catenary * Overhead contact system (OCS) * Overhead equipmen ...
in historical city areas, so preserving the city's architectural heritage. This approach may allow many new light rail city lines to replace overhead wires that are too expensive to fully route. In 2003
Mannheim Mannheim (; Palatine German: or ), officially the University City of Mannheim (german: Universitätsstadt Mannheim), is the second-largest city in the German state of Baden-Württemberg after the state capital of Stuttgart, and Germany's 2 ...
adopted a prototype light-rail vehicle (LRV) using the MITRAC Energy Saver system from
Bombardier Transportation Bombardier Transportation was a Canadian-German rolling stock and rail transport manufacturer, headquartered in Berlin, Germany. It was one of the world's largest companies in the rail vehicle and equipment manufacturing and servicing industry ...
to store mechanical braking energy with a roof-mounted supercapacitor unit. It contains several units each made of 192 capacitors with 2700 F / 2.7 V interconnected in three parallel lines. This circuit results in a 518 V system with an energy content of 1.5 kWh. For acceleration when starting this "on-board-system" can provide the LRV with 600 kW and can drive the vehicle up to 1 km without
overhead line An overhead line or overhead wire is an electrical cable that is used to transmit electrical energy to electric locomotives, trolleybuses or trams. It is known variously as: * Overhead catenary * Overhead contact system (OCS) * Overhead equipmen ...
supply, thus better integrating the LRV into the urban environment. Compared to conventional LRVs or Metro vehicles that return energy into the grid, onboard energy storage saves up to 30% and reduces peak grid demand by up to 50%. In 2009 supercapacitors enabled LRVs to operate in the historical city area of
Heidelberg Heidelberg (; Palatine German language, Palatine German: ''Heidlberg'') is a city in the States of Germany, German state of Baden-Württemberg, situated on the river Neckar in south-west Germany. As of the 2016 census, its population was 159,914 ...
without overhead wires, thus preserving the city's architectural heritage. The SC equipment cost an additional €270,000 per vehicle, which was expected to be recovered over the first 15 years of operation. The supercapacitors are charged at stop-over stations when the vehicle is at a scheduled stop. In April 2011 German regional transport operator Rhein-Neckar, responsible for Heidelberg, ordered a further 11 units. In 2009,
Alstom Alstom SA is a French multinational rolling stock manufacturer operating worldwide in rail transport markets, active in the fields of passenger transportation, signalling, and locomotives, with products including the AGV, TGV, Eurostar, Avelia ...
and RATP equipped a Citadis tram with an experimental energy recovery system called "STEEM". The system is fitted with 48 roof-mounted supercapacitors to store braking energy, which provides tramways with a high level of energy autonomy by enabling them to run without overhead power lines on parts of its route, recharging while traveling on powered stop-over stations. During the tests, which took place between the Porte d’Italie and Porte de Choisy stops on line T3 of the tramway network in Paris, the tramset used an average of approximately 16% less energy. In 2012 tram operator
Geneva Public Transport Geneva Public Transport (french: Transports publics genevois, TPG) operates most of the public transportation system in canton of Geneva, Switzerland, including the city of Geneva. The agency's head office is in Grand-Lancy, Lancy. The TPG o ...
began tests of an LRV equipped with a prototype roof-mounted supercapacitor unit to recover braking energy.
Siemens Siemens AG ( ) is a German multinational conglomerate corporation and the largest industrial manufacturing company in Europe headquartered in Munich with branch offices abroad. The principal divisions of the corporation are ''Industry'', '' ...
is delivering supercapacitor-enhanced light-rail transport systems that include mobile storage. Hong Kong's South Island metro line is to be equipped with two 2 MW energy storage units that are expected to reduce energy consumption by 10%. In August 2012 the CSR Zhuzhou Electric Locomotive corporation of China presented a prototype two-car light metro train equipped with a roof-mounted supercapacitor unit. The train can travel up 2 km without wires, recharging in 30 seconds at stations via a ground mounted pickup. The supplier claimed the trains could be used in 100 small and medium-sized Chinese cities. Seven trams (street cars) powered by supercapacitors were scheduled to go into operation in 2014 in
Guangzhou Guangzhou (, ; ; or ; ), also known as Canton () and alternatively romanized as Kwongchow or Kwangchow, is the capital and largest city of Guangdong province in southern China. Located on the Pearl River about north-northwest of Hong Kon ...
, China. The supercapacitors are recharged in 30 seconds by a device positioned between the rails. That powers the tram for up to . As of 2017, Zhuzhou's supercapacitor vehicles are also used on the new Nanjing streetcar system, and are undergoing trials in
Wuhan Wuhan (, ; ; ) is the capital of Hubei, Hubei Province in the China, People's Republic of China. It is the largest city in Hubei and the most populous city in Central China, with a population of over eleven million, the List of cities in China ...
. In 2012, in Lyon (France), the SYTRAL (Lyon public transportation administration) started experiments of a "way side regeneration" system built by Adetel Group which has developed its own energy saver named ″NeoGreen″ for LRV, LRT and metros. In 2015, Alstom announced SRS, an energy storage system that charges supercapacitors on board a tram by means of ground-level conductor rails located at tram stops. This allows trams to operate without overhead lines for short distances. The system has been touted as an alternative to the company's
ground-level power supply Ground-level power supply, also known as surface current collection or, in French, ''alimentation par le sol'' ("feeding via the ground"), is a concept and group of technologies whereby electric vehicles collect electric power at ground level fro ...
(APS) system, or can be used in conjunction with it, as in the case of the VLT network in
Rio de Janeiro Rio de Janeiro ( , , ; literally 'River of January'), or simply Rio, is the capital of the state of the same name, Brazil's third-most populous state, and the second-most populous city in Brazil, after São Paulo. Listed by the GaWC as a b ...
, Brazil, which opened in 2016.


Buses

The first hybrid bus with supercapacitors in Europe came in 2001 in
Nuremberg Nuremberg ( ; german: link=no, Nürnberg ; in the local East Franconian dialect: ''Nämberch'' ) is the second-largest city of the German state of Bavaria after its capital Munich, and its 518,370 (2019) inhabitants make it the 14th-largest ...
, Germany. It was MAN's so-called "Ultracapbus", and was tested in real operation in 2001/2002. The test vehicle was equipped with a diesel-electric drive in combination with supercapacitors. The system was supplied with 8 Ultracap modules of 80 V, each containing 36 components. The system worked with 640 V and could be charged/discharged at 400 A. Its energy content was 0.4 kWh with a weight of 400 kg. The supercapacitors recaptured braking energy and delivered starting energy. Fuel consumption was reduced by 10 to 15% compared to conventional diesel vehicles. Other advantages included reduction of emissions, quiet and emissions-free engine starts, lower vibration and reduced maintenance costs. in Luzern,
Switzerland ). Swiss law does not designate a ''capital'' as such, but the federal parliament and government are installed in Bern, while other federal institutions, such as the federal courts, are in other cities (Bellinzona, Lausanne, Luzern, Neuchâtel ...
an electric bus fleet called TOHYCO-Rider was tested. The supercapacitors could be recharged via an inductive contactless high-speed power charger after every transportation cycle, within 3 to 4 minutes. In early 2005
Shanghai Shanghai (; , , Standard Mandarin pronunciation: ) is one of the four direct-administered municipalities of the People's Republic of China (PRC). The city is located on the southern estuary of the Yangtze River, with the Huangpu River flow ...
tested a new form of
electric bus An electric bus is a bus that is propelled using electric motors as opposed to an internal combustion engine. Electric buses can store the needed electricity on-board, or be fed continuously from an external source. The majority of buses s ...
called capabus that runs without powerlines (catenary free operation) using large onboard supercapacitors that partially recharge whenever the bus is at a stop (under so-called electric umbrellas), and fully charge in the
terminus Terminus may refer to: * Bus terminus, a bus station serving as an end destination * Terminal train station or terminus, a railway station serving as an end destination Geography *Terminus, the unofficial original name of Atlanta, Georgia, United ...
. In 2006, two commercial bus routes began to use the capabuses; one of them is route 11 in Shanghai. It was estimated that the supercapacitor bus was cheaper than a lithium-ion battery bus, and one of its buses had one-tenth the energy cost of a diesel bus with lifetime fuel savings of $200,000. A hybrid electric bus called tribrid was unveiled in 2008 by the
University of Glamorgan , image_name = University of Glamorgan arms.png , image_size = 220px , caption = University of Glamorgan coat of arms , motto = Success Through Endeavour , established = , closed = , administrative_staff = , chancellor = John Morris ...
,
Wales Wales ( cy, Cymru ) is a Countries of the United Kingdom, country that is part of the United Kingdom. It is bordered by England to the Wales–England border, east, the Irish Sea to the north and west, the Celtic Sea to the south west and the ...
, for use as student transport. It is powered by
hydrogen fuel Hydrogen fuel refers to hydrogen which is burned as fuel with oxygen. It is zero-carbon, provided that it is created in a process that does not involve carbon. It can be used in fuel cells or internal combustion engines (see HICEV). Regarding hydr ...
or
solar cell A solar cell, or photovoltaic cell, is an electronic device that converts the energy of light directly into electricity by the photovoltaic effect, which is a physical and chemical phenomenon.
s, batteries and ultracapacitors.


Motor racing

The
FIA FIA is the Fédération Internationale de l'Automobile (English: International Automobile Federation), the world's governing body for all forms of motor sport where four or more wheels are used. Fia or FIA may also refer to: People * Fia Backst ...
, a governing body for motor racing events, proposed in the ''Power-Train Regulation Framework for
Formula 1 Formula One (also known as Formula 1 or F1) is the highest class of international racing for open-wheel single-seater formula racing cars sanctioned by the Fédération Internationale de l'Automobile (FIA). The World Drivers' Championship, ...
'' version 1.3 of 23 May 2007 that a new set of
power train A drivetrain (also frequently spelled as drive train or sometimes drive-train) is the group of components that deliver mechanical power from the prime mover to the driven components. In automotive engineering, the drivetrain is the components ...
regulations be issued that includes a hybrid drive of up to 200 kW input and output power using "superbatteries" made with batteries and supercapacitors connected in parallel ( KERS). About 20% tank-to-wheel efficiency could be reached using the KERS system. The
Toyota TS030 Hybrid The Toyota TS030 Hybrid is a Le Mans Prototype 1 (LMP1) sports car built by Toyota Motorsport GmbH and used by the manufacturer in the FIA World Endurance Championship in 2012 and 2013. It was Toyota's first all new prototype since the GT-One ...
LMP1 car, a
racing car Auto racing (also known as car racing, motor racing, or automobile racing) is a motorsport involving the racing of automobiles for competition. Auto racing has existed since the invention of the automobile. Races of various sorts were organise ...
developed under
Le Mans Prototype A Le Mans Prototype (LMP) is the type of sports prototype race car used in the 24 Hours of Le Mans, FIA World Endurance Championship, IMSA SportsCar Championship, European Le Mans Series and Asian Le Mans Series. Le Mans Prototypes were create ...
rules, uses a hybrid drivetrain with supercapacitors. In the 2012 24 Hours of Le Mans race a TS030 qualified with a fastest lap only 1.055 seconds slower (3:24.842 versus 3:23.787) than the fastest car, an
Audi R18 e-tron quattro The Audi R18 is a Le Mans Prototype (LMP) racing car constructed by the German car manufacturer Audi AG. It is the successor to the Audi R15 TDI. Like its predecessor, the R18 uses a TDI turbocharged diesel engine but with a reduced capacity ...
with
flywheel A flywheel is a mechanical device which uses the conservation of angular momentum to store rotational energy; a form of kinetic energy proportional to the product of its moment of inertia and the square of its rotational speed. In particular, ass ...
energy storage. The supercapacitor and flywheel components, whose rapid charge-discharge capabilities help in both braking and acceleration, made the Audi and Toyota hybrids the fastest cars in the race. In the 2012 Le Mans race the two competing TS030s, one of which was in the lead for part of the race, both retired for reasons unrelated to the supercapacitors. The TS030 won three of the 8 races in the
2012 FIA World Endurance Championship season The 2012 FIA World Endurance Championship was the inaugural running of the World Endurance Championship. It was co-organised by the Fédération Internationale de l'Automobile (FIA) and the Automobile Club de l'Ouest (ACO). The series replaced t ...
. In 2014 the
Toyota TS040 Hybrid The Toyota TS040 Hybrid is a Le Mans Prototype 1 (LMP1) sports car built and used by Toyota Motorsport GmbH in the 2014 and 2015 seasons of the FIA World Endurance Championship. Work on the car's design began in November 2012, when the Autom ...
used a supercapacitor to add 480 horsepower from two electric motors.


Hybrid electric vehicles

Supercapacitor/battery combinations in electric vehicles (EV) and
hybrid electric vehicle A hybrid electric vehicle (HEV) is a type of hybrid vehicle that combines a conventional internal combustion engine (ICE) system with an electric propulsion system ( hybrid vehicle drivetrain). The presence of the electric powertrain is intende ...
s (HEV) are well investigated. A 20 to 60% fuel reduction has been claimed by recovering brake energy in EVs or HEVs. The ability of supercapacitors to charge much faster than batteries, their stable electrical properties, broader temperature range and longer lifetime are suitable, but weight, volume and especially cost mitigate those advantages. Supercapacitors' lower specific energy makes them unsuitable for use as a stand-alone energy source for long distance driving. The fuel economy improvement between a capacitor and a battery solution is about 20% and is available only for shorter trips. For long distance driving the advantage decreases to 6%. Vehicles combining capacitors and batteries run only in experimental vehicles. all automotive manufacturers of EV or HEVs have developed prototypes that uses supercapacitors instead of batteries to store braking energy in order to improve driveline efficiency. The
Mazda 6 , commonly referred to as simply Mazda, is a Japanese multinational automotive manufacturer headquartered in Fuchū, Hiroshima, Japan. In 2015, Mazda produced 1.5 million vehicles for global sales, the majority of which (nearly one mi ...
is the only production car that uses supercapacitors to recover braking energy. Branded as i-eloop, the regenerative braking is claimed to reduce fuel consumption by about 10%. Russian Yo-cars Ё-mobile series was a concept and crossover hybrid vehicle working with a gasoline driven rotary vane type and an electric generator for driving the traction motors. A supercapacitor with relatively low capacitance recovers brake energy to power the electric motor when accelerating from a stop. Toyota's Yaris Hybrid-R concept car uses a supercapacitor to provide quick bursts of power. PSA Peugeot Citroën fit supercapacitors to some of its cars as part of its stop-start fuel-saving system, as this permits faster start-ups when the traffic lights turn green.


Gondolas

In
Zell am See Zell am See is the administrative capital of the Zell am See District in the Austrian state of Salzburg. Located in the Kitzbühel Alps, the town is an important tourist destination due to its ski resorts and shoreline on Lake Zell. While Zell a ...
,
Austria Austria, , bar, Östareich officially the Republic of Austria, is a country in the southern part of Central Europe, lying in the Eastern Alps. It is a federation of nine states, one of which is the capital, Vienna, the most populous ...
, an
aerial lift An aerial lift, also known as a cable car or ropeway, is a means of cable transport in which ''cabins'', ''cars'', ''gondolas'', or open chairs are hauled above the ground by means of one or more cables. Aerial lift systems are frequently employ ...
connects the city with
Schmittenhöhe The Schmittenhöhe is a mountain, high, on the eastern edge of the Kitzbühel Alps. It is the local mountain of the district capital of Zell am See, from where a cable car was built in 1927 by Adolf Bleichert & Co. that runs to the summit. The c ...
mountain. The gondolas sometimes run 24 hours per day, using electricity for lights, door opening and communication. The only available time for recharging batteries at the stations is during the brief intervals of guest loading and unloading, which is too short to recharge batteries. Supercapacitors offer a fast charge, higher number of cycles and longer life time than batteries. Emirates Air Line (cable car), also known as the Thames cable car, is a 1-kilometre (0.62 mi) gondola line in
London London is the capital and largest city of England and the United Kingdom, with a population of just under 9 million. It stands on the River Thames in south-east England at the head of a estuary down to the North Sea, and has been a majo ...
, UK, that crosses the
Thames The River Thames ( ), known alternatively in parts as the River Isis, is a river that flows through southern England including London. At , it is the longest river entirely in England and the second-longest in the United Kingdom, after the R ...
from the
Greenwich Peninsula The Greenwich Peninsula is an area of Greenwich in South London, South East London, England. It is bounded on three sides by a loop of the River Thames, Thames, between the Isle of Dogs to the west and Silvertown to the east. To the south is the ...
to the
Royal Docks Royal Docks is an area and a ward in the London Borough of Newham in the London Docklands in East London, England. The area is named after three docks – the Royal Albert Dock, the Royal Victoria Dock and the King George V Dock. They are mo ...
. The cabins are equipped with a modern infotainment system, which is powered by supercapacitors.


Developments

commercially available lithium-ion supercapacitors offered the highest gravimetric specific energy to date, reaching 15 Wh/kg (). Research focuses on improving specific energy, reducing internal resistance, expanding temperature range, increasing lifetimes and reducing costs. Projects include tailored-pore-size electrodes, pseudocapacitive coating or doping materials and improved electrolytes. Research into electrode materials requires measurement of individual components, such as an electrode or half-cell. By using a counterelectrode that does not affect the measurements, the characteristics of only the electrode of interest can be revealed. Specific energy and power for real supercapacitors only have more or less roughly 1/3 of the electrode density.


Market

worldwide sales of supercapacitors is about US$400 million. The market for batteries (estimated by
Frost & Sullivan Frost & Sullivan is an American business consulting firm. It offers market research and analysis, growth strategy consulting, and corporate training. It has about 45 offices in the Americas, Africa, Asia and Europe; the principal office is in Sa ...
) grew from US$47.5
billion Billion is a word for a large number, and it has two distinct definitions: *1,000,000,000, i.e. one thousand million, or (ten to the ninth power), as defined on the short scale. This is its only current meaning in English. * 1,000,000,000,000, i.e ...
, (76.4% or US$36.3 billion of which was rechargeable batteries) to US$95 billion. The market for supercapacitors is still a small niche market that is not keeping pace with its larger rival. In 2016, IDTechEx forecast sales to grow from $240 million to $2 billion by 2026, an annual increase of about 24%. Supercapacitor costs in 2006 were US$0.01 per farad or US$2.85 per kilojoule, moving in 2008 below US$0.01 per farad, and were expected to drop further in the medium term.T2+2™ Market Overview
, Ch. Ahern, Supercapacitors, 10 December 2009, Project Number NET0007IO


Trade or series names

Exceptional for electronic components like capacitors are the manifold different trade or series names used for supercapacitors, like ''APowerCap, BestCap, BoostCap, CAP-XX, C-SECH, DLCAP, EneCapTen, EVerCAP, DynaCap, Faradcap, GreenCap, Goldcap, HY-CAP, Kapton capacitor, Super capacitor, SuperCap, PAS Capacitor, PowerStor, PseudoCap, Ultracapacitor'' making it difficult for users to classify these capacitors. (Compare with #Comparison of technical parameters)


See also


Literature

* * * * * * * * * * *


References


External links


Supercapacitors: A Brief Overview
pub 2003 {{DEFAULTSORT:Electric Double-Layer Capacitor Capacitors Emerging technologies Energy conversion ja:電気二重層コンデンサ zh:双电层电容器