谭震¹,王崇²,徐东彦¹,陈剑²

• 1:青岛科技大学 化工学院，山东 青岛 266042
• 2:中科院 大连化学物理研究所，辽宁 大连 116023

摘要(Abstract)：

锂硫电池是目前已知的比能量最高的以固态材料为活性物质的二次电池。然而，多硫化物"穿梭"效应导致的容量衰减快、库仑效率低和自放电率高等问题限制了锂硫电池的实用化进程。通过测试电池搁置前后的放电容量，分析了锂硫软包电池的放电深度（DOD）、环境温度和搁置时间对电池自放电特性的影响。研究结果表明，不同DOD下锂硫电池具有不同的自放电特性，自放电与环境温度、搁置时间呈正相关性。采用原位四电极法考察了不同DOD时内部电解液电导率的变化情况，推测锂硫电池的自放电特性与锂硫电池的电化学反应机制和过程产物密切相关。

关键词(KeyWords)： 锂硫电池;自放电;影响因素;多硫化物;电解液电导率

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 谭震¹,王崇²,徐东彦¹,陈剑²

DOI: 10.3969/j.issn.1003-9015.2017.04.031

参考文献(References)：

• [1] Marom R, Amalraj S F, Leifer N, et al. A review of advanced and practical lithium battery materials[J]. Journal of Materials Chemistry, 2011, 21(27):9938-9954.
  [2] ZUO Peng-jian (左朋建), YIN Ge-ping (尹鸽平). Si-Mn composite anode used for Li-ion battery (锂离子电池用Si-Mn复合电极的研究)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2006, 20(4):634-637.
  [3] Manthiram A, Fu Y, Su Y S. Challenges and prospects of lithium-sulfur batteries[J]. Accounts of Chemical Research, 2013, 46(5):1125-34.
  [4] Fotouhi A, Auger D J, Propp K, et al. A review on electric vehicle battery modelling:from lithium-ion toward lithium-sulphur[J]. Renewable & Sustainable Energy Reviews, 2016, 56:1008-1021.
  [5] Li K, Wang B, Su D, et al. Enhance electrochemical performance of lithium sulfur battery through a solution-based processing technique[J]. Journal of Power Sources, 2012, 202:389-393.
  [6] Ahn W, Kim K B, Jung K N, et al. Synthesis and electrochemical properties of a sulfur-multi walled carbon nanotubes composite as a cathode material for lithium sulfur batteries[J]. Journal of Power Sources, 2012, 202:394-399.
  [7] Barchasz C, Leprêtre J C, Alloin F, et al. New insights into the limiting parameters of the Li/S rechargeable cell[J]. Journal of Power Sources, 2012, 199:322-330.
  [8] Manthiram A, Chung S H, Zu C. Lithium-sulfur batteries:progress and prospects[J]. Advanced Materials, 2015, 27(12):1980-2006.
  [9] Knap V, Stroe D I, Swierczynski M, et al. Investigation of the self-discharge behavior of lithium-sulfur batteries[J]. Journal of the Electrochemical Society, 2016, 163(6):A911-A916.
  [10] Lacey M J, Yalamanchili A, Maibach J, et al. The Li-S battery:an investigation of redox shuttle and self-discharge behaviour with LiNO₃-containing electrolytes[J]. Rsc Advances, 2015, 6(5):3632-3641.
  [11] Xu W T, Peng H J, Huang J Q, et al. Towards stable lithium-sulfur batteries with a low self-discharge rate:ion diffusion modulation and anode protection[J]. Chemsuschem, 2015, 8(17):2892-2901.
  [12] Al-Mahmoud S M, Dibden J W, Owen J R, et al. A simple, experiment-based model of the initial self-discharge of lithium-sulphur batteries[J]. Journal of Power Sources, 2016, 306:323-328.
  [13] XIONG Shi-zhao (熊仕昭), XIE Kai (谢凯), HONG Xiao-bin (洪晓斌), et al. Effects of temperature and additive on self-discharge of lithium-sulfur batteries (温度和添加剂对锂硫电池自放电的影响)[J]. Chinese Battery Industry (电池工业), 2010, 15(6):363-366.
  [14] Cheon S E, Ko K S, Cho J H, et al. Rechargeable lithium sulfur battery I. structural change of sulfur cathode during discharge and charge[J]. Journal of the Electrochemical Society, 2003, 150(6):A796-A799.
  [15] LIN Cheng-tao (林成涛), WANG Jun-ping (王军平), CHEN Quan-shi (陈全世). Methods for state of charge estimation of EV batteries and their application (电动汽车SOC估计方法原理与应用)[J]. Battery Bimonthly (电池), 2004, 34(5):376-378.
  [16] Roscher M A, Sauer D U. Dynamic electric behavior and open-circuit-voltage modeling of LiFePO₄-based lithium ion secondary batteries[J]. Journal of Power Sources, 2011, 196:331-336.
  [17] Ryu H S, Ahn H J, Kim K W, et al. Self-discharge characteristics of lithium/sulfur batteries using TEGDME liquid electrolyte[J]. Electrochimica Acta, 2006, 52(4):1563-1566.
  [18] XU Xin-ge (徐欣歌), YANG Song (杨松), LI Yan-fang (李艳芳), et al. A method of SOC-estimate based on forecast of open-circuit voltage(一种基于预测开路电压的SOC估算方法)[J]. Electronic Design Engineering(电子设计工程), 2011, 19(14):127-129.
  [19] Choi J W, Kim J K, Cheruvally G, et al. Rechargeable lithium/sulfur battery with suitable mixed liquid electrolytes[J]. Electrochimica Acta, 2007, 52(5):2075-2082.
  [20] Chang D R, Lee S H, Kim S W, et al. Binary electrolyte based on tetra(ethylene glycol) dimethyl ether and 1,3-dioxolane for lithium-sulfur battery[J]. Journal of Power Sources, 2002, 112(2):452-460.
  [21] Zhang S S. Liquid electrolyte lithium/sulfur battery:Fundamental chemistry, problems, and solutions[J]. Journal of Power Sources, 2013, 231:153-162.
  [22] XIONG Shi-zhao (熊仕昭), XIE Kai (谢凯), HONG Xiao-bin (洪晓斌). Effect of LiNO₃ as additive on electrochemical properties of lithium-sulfur batteries (硝酸锂作添加剂对锂硫电池电化学性能的影响)[J]. Chemical Journal of Chinese Universities (高等学校化学学报), 2011, 32(11):2645-2649.
  [23] JIN Zhao-qing (金朝庆), XIE Kai (谢凯), HONG Xiao-bin (洪晓斌). Review of electrolyte for lithium sulfur battery (锂硫电池电解质研究进展)[J]. Acta Chimica Sinica (化学学报), 2014, 72(1):11-20.
  [24] MA Yu-lin (马玉林), GAO Yun-zhi (高云智), ZUO Peng-jian (左朋建). Effect of triphenyl phosphate on the safety and electrochemical performance of lithium ion batteries (磷酸三苯酯对锂离子电池安全性及电化学性能的影响)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2010, 24(6):954-959.