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in the 1970s. The principle of the RF battery system was presented by L. H. Thaller of the National Aeronautics and Space Administration (NASA) of the United States in 1974(1). NASA mainly conducted research on the Fe/Cr system, discontinuing it in 1984 with the publication of the Final Report(5). At the same time in Japan, the Electrotechnical Lab. (ETL; currently the National Institute of Advanced Industrial Science and Technology) was conducting basic research, and the development of the Fe/Cr system made progress as a project of the New Energy and Industrial Technology Development Organization (NEDO). In about 1985, in Australia, the University of New South Wales (UNSW) proceeded to develop the V system. Concerning the practical use of RF batteries, electric power companies and manufacturers in Japan jointly con- ducted research with enthusiasm, and in about 2001, the V system was partially put into practical use. The summary of the development of the Fe/Cr system and V system is explained below: Table 2. History of RF Battery Development ducted basic research on many possible redox pairs, and proceeded with practical research into the Fe/Cr system using hydrochloric acid solution(6)-(10). Along with these elemental technology developments, Mitsui Engineering and Shipbuilding Co., Ltd. (MES) manufactured and tested 10 kW and 60 kW system proto- types as part of the NEDO project during 1984 to 1987(11). Kansai Electric Power Co., Inc. (KEPCO) and Sumitomo Electric Industries, Ltd. (Sumitomo Electric) also started to develop RF batteries in 1985 on their own, and tested a 60 kW class Fe/Cr system RF battery in 1989(12), (13). The Fe/Cr system has the following problems: the Cr ions’ electrode reaction is slow; because the different metal ions are used in positive and negative reactions, each ion is mixed through the membrane and thus gradually de- crease the battery capacity; the Cr ions’ redox potential is close to the hydrogen gas generation potential and a small amount of hydrogen gas is generated from the negative electrode near the end of the charge, thereby reducing the battery capacity because of differences in the SOC between the positive and negative electrodes. KEPCO and Sumit- omo Electric theoretically solved the problem of the mix- ture of redox ions between the positive and negative electrodes by using a single-fluid Fe/Cr system(14) in which Fe ions and Cr ions are mixed in both the positive and neg- ative electrodes. To solve the problem of the generation of hydrogen gas, the electrode characteristics were improved, and various types of accessories known as rebalancing systems, which adjust the SOC for both the positive and negative electrodes in the long run, were proposed. With the aim of improving the energy density of the Fe/Cr system, MES replaced Fe ions with Br ions for the positive electrode, and researched into Cr/Br systems(15). Likewise, the ETL and Ebara Corp. jointly investigated the feasibility of the Cr/Cl system(16). Furthermore, the V/O2 system, in which air is used on the positive electrode, was studied(17). (2) Vanadium system (V/V system) In Australia, where vanadium resources are abun- dantly available, Prof. Maria Kazacos of the UNSW pro- posed V system RF batteries, which use V ions at both the positive and negative electrodes, around 1985(18)-(20), and applied for a basic patent in 1986(21). In Japan, which has no natural vanadium resources, V system RF batteries were not researched into enthusiastically for economic reasons. However, Kashima Kita Electric Power Corp. (Kashima Kita) and the ETL. developed the technology of recovering vanadium included in petroleum and heavy fuels from the soot of the fuels burned at thermal power plants. Thus the economic value of V system RF batteries was reviewed and their development started in the country(22). The electro- motive force of the V system was approximately 1.4 V, which was 1.4 times as large as that of the Fe/Cr system, so that, provided that the cells and energy efficiency were the same, the output was double. Because the electrode reac- tion of V ions was comparatively fast in practical use, the output was found to be several times as large. The system used V ions at both the positive and negative electrodes; therefore, even if ions were mixed between the positive and negative electrodes through the membrane, the battery ca- pacity did not decrease, in contrast to the Fe/Cr system. 1949 Kangro (German patent): Cr/Cr and other systems 1974 Battelle: Cr/Cr, Fe/Cr, V, Mo, Mn and other systems 1974 NASA released the principle of the RF battery—U.S. basic patent (’75) • Fe/Cr system 1 kW (’78), Final Report (’84) ETL started the research and development of RF Battery. 1980 NEDO (Moonlight Project) established the project “Advanced Battery Electric Power Storage System.” • RF (ETL./Mitsui Engineering and Shipbuilding [MES]), NaS (Yuasa Battery), Zn/Br (Meidensha), and Zn/Cl2 (Furukawa Electric) • ETL, Fe/Cr system, 1 kW (’82); MES, 60 kW (’84 to’87) NEDO (Sunshine Project) • RF battery for solar power generation (MES and Ebara) 1985 University of New South Wales (UNSW; Australia) released the V system RF battery and applied a basic patent (’86). 1989 ETL. and Kashima Kita Electric Power developed V system RF battery for the use of vanadium from the soot • V system, 1 kW (Ebara, ’90); 10 kW (MES, ’91); 200 kW (Kashima Kita, ’97) KEPCO and Sumitomo Electric • Fe/Cr system, 60 kW (’89); V system (450 kW, ’96) 1998 ETL. and Kashima Kita • 10 kW Redox Super Capacitor on-vehicle test 2001 Sumitomo Electric put V system RF battery into practical use (for load leveling, instantaneous voltage sag compensation and emergency use). NEDO verified the RF battery for stabilizing the wind power output fluctuation. Sumitomo Electric: 170 kW (’00), 6 MW (’05) 2011 The development of RF batteries is proceeding worldwide, including in the U.S., Europe and China. (1) Iron–Chromium (Fe/Cr) system Around 1980 in Japan, expectations grew regarding the development of large-capacity energy storage batteries that would complement pumped hydro energy storage to improve the load factor, which was getting lower at that time, by load leveling. In NEDO’s Moonlight Project, the development of four advanced batteries, including RF, sodium/sulfur, zinc/bromine, and zinc/chlorine batteries, started. Among the batteries, research into RF batteries was conducted mainly by the ETL(12). The laboratory con- SEI TECHNICAL REVIEW · NUMBER 73 · OCTOBER 2011 · 7PDF Image | Redox Flow Battery for Energy Storage
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