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LiFePO4在不同pH值水溶液中电化学性能表现及其衰减机理
尹元,文越华*,卢咏来*,程杰,曹高萍,杨裕生
作者单位E-mail
尹元 北京化工大学材料科学与工程学院北京100029防化研究院, 北京100191  
文越华* 防化研究院, 北京100191 wen_yuehua@126.com 
卢咏来* 北京化工大学材料科学与工程学院北京100029 luyonglai@mail.buct.edu.cn 
程杰 防化研究院, 北京100191  
曹高萍 防化研究院, 北京100191  
杨裕生 防化研究院, 北京100191  
摘要:
LiFePO4在含Li+水溶液中的电化学性能稳定性与水溶液的pH值密切相关,当溶液的pH值达到11后LiFePO4在充放电循环过程中的容量衰减十分明显. 通过循环伏安测试、交流阻抗测试、电极充放电性能测试、非原位X射线衍射测试以及化学分析的方式对其容量衰减机理进行了研究. 结果表明LiFePO4在pH=7的LiNO3水溶液中具有相对最高的电化学稳定性,但是LiFePO4材料在水溶液中较之其在有机电解液中依然会有较差的电化学性能表现. 认为LiFePO4在水介质中的容量衰减现象归因于其在持续充放电过程中的Li、Fe、P溶解,同时电极表面也会附着一层沉淀物. 这些最终导致了材料晶体结构的破坏、电极极化的增大以及电极容量的衰减.
关键词:  LiFePO4,水溶液,电化学性能,容量衰减,机理
DOI:10.1063/1674-0068/28/cjcp1502020
分类号:
基金项目:
Electrochemical Performance and Capacity Fading Mechanism of LiFePO4 at Different pH Aqueous Electrolyte Solutions
Yuan Yin,Yue-hua Wen*,Yong-lai Lu*,Jie Cheng,Gao-ping Cao,Yu-sheng Yang
Abstract:
The electrochemical stability of LiFePO4 in a Li+-containing aqueous electrolyte solution is critically dependent on the pH value of the aqueous solution. It shows a considerable decay in capacity of LiFePO4 upon cycling when the pH value is increased to 11. The mechanism responsible for the capacity fading is extensively investigated by means of cyclic voltammogram, ac impedance, charge/discharge, ex situ X-ray diffraction, and chemical analysis. LiFePO4 is relatively electrochemically stable in LiNO3 aqueous solution with pH=7. But the electrochemical performance of LiFePO4 in aqueous electrolyte is inferior to that in organic electrolyte. It is attributed to the loss of Li and the Fe, P dissolution during prolonged charge-discharge in aqueous medium. A precipitate is formed on the surface of LiFePO4 electrodes. It results in the change of crystalline structure, a large electrode polarization, and capacity fading.
Key words:  Olivine LiFePO4, Aqueous electrolyte, Electrochemical property, Capacity fade, Mechanism