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EPRI Proprietary Licensed Material Cell Life Prediction The life of a particular type of capacitor cell can be determined by testing a number of cells at a variety of temperature and voltage conditions. Capacitor failure is usually defined as a certain percentage loss of capacitance, increase in series resistance, or increase in leakage current. Also complete failure can occur due to an open or short circuit. Note that charge/discharge cycling is not a first-order determinant of cell life unless the cycle rate causes cell overheating. See the Appendix for a discussion of predicting capacitor life and cell failure mode flow charts. Development History, Status, and Plans Brief 25-year Product History The concept of storing electrical energy in the electric double surface layer that is naturally formed at the interface between an electrolyte and a solid has been known since the late 1800’s. General Electric reported the first two-terminal device based on this charge-storage mechanism in 1957. In 1962, Standard Oil of Ohio filed a patent application for a practical energy storage device based on charge storage in an electric double layer. The patent, awarded in November 1966, formed the basis for subsequent patents and eventual licensing. New ideas with configurations ruled to be outside these early patents have resulted in patents by numerous business entities around the world. One of the earliest electrochemical capacitor products to be introduced was by Nippon Electric Corporation (NEC) under license from Standard Oil of Ohio (SOHIO) in August 1978. NEC created the name Supercapacitor and has used it as the name of their electrochemical capacitor product family. Production proceeded with the start of mass production in January, 1980, and sales to the Japanese market. In 1982, NEC introduced a new line of electrochemical capacitors having a different design optimization. This was repeated again in 1983, in 1987, and again in 1988. In general, each of these type I product lines was optimized for a different application. Large capacitors now under development by NEC are aimed at the automotive market. One very interesting feature of the NEC product is the use of bipolar construction. NEC developed processes to assemble six or more cells in a series-stack and successfully seal the perimeter of the device. This is significant because it eliminated the need for external cell interconnects as is required with single-cell construction. This same approach has been used in large capacitors manufactured by ECOND and ELIT. Panasonic started manufacturing their Goldcap electrochemical capacitor in 1978. The two major differences between the Panasonic and the NEC products were the electrolyte and the construction. The Panasonic Goldcap has a type II design. It uses an organic electrolyte with a spiral-wound single-cell construction. Early Panasonic products were rated at
EPRI Proprietary Licensed Material Maxwell Technologies began development efforts on electrochemical capacitors in the early 1990’s after receiving a DOE contract to develop an advanced electric vehicle loadleveling capacitor. Development was initially confined to type I products, then switched to type II products in an effort to obtain higher energy density. Maxwell has developed 8-kJ cells using an accordion-fold design with carbon cloth electrodes and organic electrolyte. They presently are developing a spiral-wound design using particulate carbon. At about the same time in Japan, the Okamura Laboratory begin working on a type II design that used active power electronics for controlling and leveling multi-cell modules. Several patents have been obtained in Japan and the US. Results of this work were first published in English at the electric vehicle conference, EVS-13 in 1996, and some time later at the International Seminar on Double Layer Capacitors held annually in south Florida. The design technique, under the trademark ECaSS, has led to relatively high reported specific energies in the 4-6 Wh/kg range. Several Japanese manufactures including Shizuki Electric, Nissan Diesel and Power Systems Ltd, offer either capacitor modules or products that use this design. The first reported activity on type III capacitors was from Russia. The Elit Company made asymmetric capacitors based on nickel oxyhydroxide and carbon electrodes with potassium hydroxide electrolyte. These devices were used to power wheel chairs and subsequently, children’s toy cars. This company later concentrated on, and has widely commercialized a type I carbon/carbon electrochemical capacitor. The Russian company ECOND presented a paper in the US in late 1993 that described type I electrochemical capacitors much larger in size than any device then available or under development in the US. Their capacitors were described as the power source for starting diesel internal combustion engines of sizes up to 3000 horsepower, including locomotive engines. The 1993 paper was certainly an eye-opener for some US researchers involved in the development of 1.8 MJ electric vehicle load-leveling capacitors. As with ELIT, this work was a giant step ahead of research that had been reported in the US and provided encouragement to many capacitor developers. Type III development activities continued in Russia and were greatly expanded by the Joint Stock Company ESMA, a Moscow-based developer and manufacturer. This company reported using type III capacitors to power electric buses and electric trucks in 1997, with capacitors being the sole energy source in the vehicles. These 30 MJ capacitor storage systems far surpassed the size of any previously reported system. ELTON, the ESMA parent company, has patents that cover the asymmetric capacitor concept, i.e. type III and IV designs. There is considerable development activity today on type IV capacitor products. These include use of lithium battery intercalation electrodes in combination with activated carbon double-layer charge storage electrodes. Development along this line has progressed rapidly due to the exploitation of material advances made on Li-ion battery technology. Electrochemical Capacitors 23
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