A supercapacitor (SC), also called an ultracapacitor, is a high-capacity capacitor, with a capacitance value much higher than solid-state capacitors but with lower voltage limits. It bridges the gap between electrolytic capacitors and rechargeable batteries. It typically stores 10 to 100 times more energy per unit mass or energy per unit volume than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more charge and discharge cycles than rechargeable batteries.
Unlike ordinary capacitors, supercapacitors do not use a conventional solid dielectric, but rather, they use electrostatic double-layer capacitance and electrochemical pseudocapacitance, both of which contribute to the total energy storage of the capacitor.
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 they are used for regenerative braking, short-term energy storage, or burst-mode power delivery. Smaller units are used as power backup for static random-access memory (SRAM).
Background
The electrochemical charge storage mechanisms in solid media can be roughly (with some overlap) classified into 3 types:
Electrostatic double-layer capacitors (EDLCs) use carbon electrodes or derivatives with much higher electrostatic double-layer capacitance than electrochemical pseudocapacitance, achieving separation of charge in a Helmholtz double layer at the interface between the surface of a conductive electrode and an electrolyte. The separation of charge is of the order of a few ångströms (0.3–0.8 nm), much smaller than in a conventional capacitor. The electric charge in EDLCs is stored in a two-dimensional interphase (surface) of an electronic conductor (e.g. carbon particle) and ionic conductor (electrolyte solution). Batteries with solid electroactive materials store charge in bulk solid phases by virtue of redox chemical reactions. Electrochemical supercapacitors (ECSCs) fall in between EDLCs and batteries. ECSCs use metal oxide or conducting polymer electrodes with a high amount of electrochemical pseudocapacitance additional to the double-layer capacitance. Pseudocapacitance is achieved by Faradaic electron charge-transfer with redox reactions, intercalation or electrosorption.
In solid-state capacitors, the mobile charges are electrons, and the gap between electrodes is a layer of a dielectric. In electrochemical double-layer capacitors, the mobile charges are solvated ions (cations and anions), and the effective thickness is determined on each of the two electrodes by their electrochemical double layer structure. In batteries the charge is stored in the bulk volume of solid phases, which have both electronic and ionic conductivities. In electrochemical supercapacitors, the charge storage mechanisms either combine the double-layer and battery mechanisms, or are based on mechanisms, which are intermediate between true double layer and true battery.
History
In the early 1950s, General Electric engineers began experimenting with porous carbon electrodes in the design of capacitors, from the design of fuel cells and rechargeable batteries. Activated charcoal is an electrical conductor that is an extremely porous "spongy" form of carbon with a high specific surface area. In 1957 H. Becker developed a "Low voltage electrolytic capacitor with porous carbon electrodes"..A brief history of supercapacitors, Autumn 2007, Batteries & Energy Storage Technology. . 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 designs..J. G. Schindall, The Change of the Ultra-Capacitors, IEEE Spectrum, November 2007 . 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, 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, 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 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 marketed its Goldcaps brand.Panasonic, Electric Double Layer Capacitor, Technical guide,1. Introduction,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 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 (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. In 1994 using the anode of a 200 V high-voltage tantalum electrolytic capacitor, David A. Evans developed an "Electrolytic-Hybrid Electrochemical Capacitor"..David A. Evans (Evans Company): High Energy Density Electrolytic-Electrochemical Hybrid Capacitor . In: Proceedings of the 14th Capacitor & Resistor Technology Symposium. 22 March 1994. 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 (ruthenium (IV) oxide) cathode from an electrochemical capacitor, yielding a hybrid electrochemical capacitor. Evans' capacitors, coined Capattery,Evans Capacitor Company 2007 Capattery series 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 capacitors. These hybrid capacitors were pioneered by Fujitsu'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 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 and . The total capacitance is given by the formula
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 , then ). For asymmetric capacitors, the total capacitance can be taken as that of the electrode with the smaller capacitance (if , then ).
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, electrostatic storage of the electrical energy achieved by separation of charge in a Helmholtz double layer. Pseudocapacitance, electrochemical storage of the electrical energy. The original type uses faradaic redox 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. 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 electrode surface and an adjacent liquid electrolyte. In this interface occurs a very special phenomenon of the double layer effect.