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Mössbauer study of new vanadate glass with large charge-discharge capacity
Authors:Shiro Kubuki  Hitomi Masuda  Koken Matsuda  Kazuhiko Akiyama  Ayuko Kitajo  Shigeto Okada  Péter Zsabka  Zoltán Homonnay  Ernõ Kuzmann  Tetsuaki Nishida
Institution:1. Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, Minami-Osawa 1-1, Hachi-Oji, Tokyo, 192-0397, Japan
2. Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga koen 6-1, Kasuga, Fukuoka, 816-8580, Japan
3. Institute of Chemistry, Faculty of Science, E?tv?s University, Pázmány P.s. 1/A, Budapest, 1117, Hungary
4. Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science and Engineering, Kinki University, Kayanomori 11-6, Iizuka, Fukuoka, 820-8555, Japan
Abstract:Charge-discharge capacity and cyclicity of lithium ion battery (LIB) was evaluated in which 15Li2O·10Fe2O3·xSnO2·5P2O5·(70–x)V2O5 glass (x?=?0 and 20 in mol%, abbreviated as xLFSPV) was used as a cathode. A local structure of xLFSPV glass before and after charging was investigated by 57Fe- and 119Sn-Mössbauer spectroscopies. 57Fe-Mössbauer spectrum of xLFSPV glass with ‘x’ of 20 was composed of a doublet with isomer shift (δ) of 0.35±0.02 mm s???1 and quadrupole splitting (Δ) of 0.88±0.03 mm s???1 due to distorted FeIIIO4 tetrahedra. 119Sn-Mössbauer spectrum of this glass consisted of a doublet with δ of 0.08±0.01 and Δ of 0.52±0.01 mms???1 due to distorted SnVIO6 octahedra. After discharging the battery from 4.5 to 1.0 V, larger δ of 0.40±0.03 mm s???1 and Δ of 0.94±0.04 mm s???1 were obtained, indicating that both iconicity of Fe-O bonds and local distortion of FeIIIO4 tetrahedra were increased. On the contrary, identical δ of 0.09±0.01 mm s???1 and Δ of 0.50±0.01 mm s???1 were observed in the 119Sn-Mössbauer spectrum of 20LFSPV glass after the discharge, indicating that chemical environment of SnIVO6 octahedra was not affected after the discharge. Charge-discharge curve of LIB containing 20LFSPV glass as a cathode active material recorded under the current density of 8.3 mA g???1 (0.011 mA cm???2) between 1.0 and 4.5 V showed a large initial charge capacity of 431.1 mAh g???1 and discharge capacity of 382.3 mAh g???1, respectively. These results indicate that 20LFSPV glass could be a new cathode active material for LIB.
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