成果報告書詳細
管理番号20150000000238
タイトル*平成26年度中間年報 革新型蓄電池先端科学基礎研究事業 革新型蓄電池先端科学基礎研究開発 (10)
公開日2015/5/26
報告書年度2014 - 2014
委託先名公立大学法人兵庫県立大学
プロジェクト番号P09012
部署名スマートコミュニティ部
和文要約
英文要約 In this study, cathode and electrolyte materials used for the batteries based on fluoride shuttle are investigated in detail. The effect of the addition of various metal fluorides on the charge-discharge behaviors of Fluoride A in solid state cells were studied. On the other hand, in case of the electrolyte material, factors affecting the conductivity and the electrochemical behaviors of LaF3 based materials were investigated.

The effect of the addition of metal fluorides to fluoride A
The discharge capacity of fluoride A in the absence of metal fluoride B was almost 0 at 50°C, however, the addition of appropriate amounts of it facilitated the discharge of fluoride A at around 0.5V, when Pb metal was used as an anode material. This voltage was slightly higher than that observed for fluoride A, suggesting that some intermediate materials were formed between fluoride A and B. The discharge capacity at the 1st cycle reached 700mAh/g. Oxidation of the discharged product of fluoride A occurred at around 1.6 V and the charge capacity reached 680mAh/g.

The effect of the addition of metal fluorides to element C
When metal fluorides B and D were added to element C, it was charged at around 1.6V. The discharge capacity greatly varied depending on the ratio of fluoride B and element C and reached 420 mAh/g. Raman, XRD and XPS analyses of the charged product indicated that fluoride D was inserted into element C together with fluoride ions.

Factors affecting the conductivity of LaF3 based electrolyte
When LaF3 based electrolyte pellets prepared by CIP method were heated under dry Ar atmosphere, the ionic conductivity reached 1.1-10-5 S cm-1 at 50°C which was very similar to that reported for single crystal. This is ascribed to the decrease in the grain boundary resistance. Similar high conductivities were achieved for the samples treated under very high pressure of 700 MPa.

Electrochemical behaviors of LaF3 based electrolyte
When the electrolytes obtained above were anodically polarized at 150°C, a large current due to the reduction of La was observed below -2.6 V vs Pb/PbF2. An oxidation current due to the formation of La metal was also observed at -2.2 V. These indicate that these electrolytes would be available for the batteries based on fluoride shuttle with high voltage.
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