全固态锂离子电池硫化物电解质的研究进展

摘要

目前，锂离子电池已经广泛地应用于交通、通讯、便携式电子产品及电动工具等领域。传统的锂离子电池采用液体电解液，存在易挥发、易泄漏、抗冲击性能差等缺点，存在安全隐患。全固态电解质具有热稳定性高、循环寿命长、抗震动性能好等优点，是锂离子电池取代液体电解液的一种理想替代方案。硫化物电解质体系具有离子导电率高、制备简便、电化学窗口宽等优点，已经成为全固态锂离子电池的研究热点。综述了全固态锂电池Li₂S-P₂S₅基电解质的最新研究进展，总结了各种性能改进方法，并对其应用前景做了展望。

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	徐强
	莫珊珊
	徐志彬
	刘佳荃
	丁飞
	刘兴江

关键词：全固态锂离子电池；硫化物电解质；机械球磨；离子电导率；化学稳定性

Abstract：

Recently, lithium-ion batteries have been widely used in the field of transportation, communication, portable electronics and electric tools, etc. Traditional lithium ion batteries pose a lot of safety hazards by using liquid electrolyte, such as volatility, easy to leak, poor impact resistance, etc. All-solid-state electrolyte, which has the property of high thermal stability, long cycle life, shock resistant performance, is an ideal alternative material to replace the liquid electrolyte. The sulfide electrolyte with many advantages, including high ionic conductivity, simple preparation, wide electrochemical window, has become a research focus of all-solid-state lithium ion batteries recently. The progress of Li₂S-P₂S₅ based electrolytes of all-solid-state lithium-ion battery is introduced in this paper. The latest research results and various improvements of battery performance are summarized, and the prospect of application for the sulfide electrolyte in the future is also discussed.

Keywords： all-solid-state lithium-ion battery； sulfide electrolyte； mechanical ball-milling； ionic conductivity； chemical stability

Received 2015-04-12;

Corresponding Authors: 徐强,E-mail:xuqiang@tju.edu.cn。 Email: xuqiang@tju.edu.cn

About author: 徐强(1967-),男,副教授,主要研究方向为先进化学电源。

引用本文:

徐强, 莫珊珊, 徐志彬, 刘佳荃, 丁飞, 刘兴江.全固态锂离子电池硫化物电解质的研究进展[J]. 化学工业与工程, 2017,34(3): 50-57

Xu Qiang, Mo Shanshan, Xu Zhibin, Liu Jiaquan, Ding Fei, Liu Xingjiang.Research Progress on Sulfide Electrolyte for All-Solid-State Lithium Batteries[J]. Chemcial Industry and Engineering, 2017,34(3): 50-57

[1] 刘晋,徐俊毅,林月,等. 全固态锂离子电池的研究及产业化前景[J]. 化学学报, 71: 869-878 Liu Jin, Xu Junyi, Lin Yue, et al. All-Solid-State lithium ion battery: Research and industrial prospects[J]. Acta Chimical Sinica, 71: 869-878(in Chinese)
[2] 李杨, 连芳, 周国治. 应用于锂离子电池的无机晶态固体电解质导电性能研究进展[J]. 硅酸盐学报, 2013, 41(7): 950-958 Li Yang, Lian Fang, Zhou Guozhi. Conductive performance of inorganic crystalline solid electrolytes used in lithium ion batteries-a short review[J]. Journal of the Chinese Ceramic Society, 2013, 41(7): 950-958(in Chinese)
[3] 张舒,王少飞,凌世刚,等. 锂离子电池基础科学问题(X)——全固态锂离子电池[J]. 储能科学与技术,2014,3(4): 376-394 Zhang Shu, Wang Shaofei, Ling Shigang, et al. Fundamental scientific aspects of lithium ion batteries(X)—All-solid-state lithium-ion batteries[J]. Energy Storage Science and Technology, 2014, 3(4): 376-394(in Chinese)
[4] Takada K. Progress and prospective of solid-state lithium batteries[J]. Acta Materialia, 2013, 61: 759-770
[5] Ohtomo T, Hayashi A, Tatsumisago M, et al. All-Solid-State lithium secondary batteries using the 75Li₂S·25P₂S₅ glass and the 70Li₂S·30P₂S₅ glass-ceramic as solid electrolytes[J]. Journal of Power Sources, 2013, 233: 231-235
[6] Kanno R, Murayama M. Lithium ionic conductor thio-LISICON[J]. Journal of the Electrochemical Society, 2001, 148(7): A742-A746
[7] Yang J, Huang Z, Huang B, et al. Influence of phosphorus sources on lithium ion conducting performance in the system of Li₂O-Al₂O₃-GeO₂-P₂O₅ glass-ceramics[J]. Solid State Ionics, 2015, 270: 61-65
[8] Wang Y, Liu Z, Zhu X, et al. Highly lithoum-ion conductive thio-LISICON thin film processed by low-temperature solution method[J]. Journal of Power Sources, 2013, 224: 225-229
[9] Hayashi A, Hama S, Morimoto H, et al, Preparation of Li₂S-P₂S₅ amorphous solid electrolytes by mechanical milling[J]. Journal of the American Ceramic Society, 2001, 84(2): 477-479
[10] Hayashi A, Yamashita H, Tatsumisago M, et al. Characterization of Li₂S-SiS₂-Li_xMO_y (M=Si, P, Ge) amorphous solid electrolytes prepared by melt-quenching and mechanical milling[J]. Solid State Ionics, 2002, 148: 381-389
[11] Knauth P. Ionic solid Li ion conductors: An overview[J]. Solid state Ionics, 2009, 180: 911-916
[12] Kim J, Yoon Y, Lee J, et al. Formation of high lithium ion conducting phase mechanically milled amorphous Li₂S-P₂S₅ system[J]. Journal of Power Sources, 2011, 196: 6 920-6 923
[13] Tatsumisago M, Hayashi A. Superionic glasses and glass-ceramics in the Li₂S-P₂S₅ system for all-solid-state lithium secondary batteries[J]. Solid State Ionics, 2012, 225: 342-345
[14] Ong S P, Mo Y F, Richards W D. Phase stability, electrochemical stability and ionic conductivity of the Li_10±1MP₂X₁₂ (M=Ge, Si, Sn, Al or P, and X=O, S, or Se) family of superionic conductor[J]. Energy & Environmental Science, 2013, 6: 148-156
[15] Minami K, Hayashi A, Tatsumisago M. Preparation and characterization of lithium ion conducting Li₂S-P₂S₅-GeS₂ glasses and glass-ceramics[J]. Journal of Non-Crystalline Solids, 2010, 356: 2 666-2 669
[16] Trevey J E, Jung Y S, Lee S H. Preparation of Li₂S-GeS₂-P₂S₅ electrolyte by a single step ball milling for all-solid-state lithium secondary batteries[J]. Journal of Power Sources, 2010, 195: 4 984-4 989
[17] Minami K, Hayashi A, Ujiie S, et al. Electrical and electrochemical properties of glass-ceramic electrolytes in the systems Li₂S-P₂S₅-P₂S₃ and Li₂S-P₂S₅-P₂O₅[J]. Solid State Ionics, 2011, 192: 122-125
[18] Ooura Y, Machida N, Uehara T, et al. A new lithium-ion conducting glass ceramic in the composition of 75Li₂S-5P₂S₃-20P₂O₅(mol% )[J]. Solid State Ionics, 2014, 262: 733-737
[19] Ooura Y, Machida N, Naito M, et al. Electrochemical properties of amorphous solid electrolytes in the system Li₂S-Al₂S₃-P₂S₅[J]. Solid State Ionics, 2012, 225: 350-353
[20] Ujiie S, Hayashi A, Tatsumisago M. Structure, ionic conductivity and electrochemical stability of Li₂S-P₂S₅-LiI glass and glass-ceramic electrolyte[J]. Solid State Ionics, 2012, 211: 42-45
[21] Ujiie S, Hayashi A, Tatsumisago M. Preparation and ionic conductivity of (100-x)(0.8Li₂S·0.2P₂S₅)·xLiI glass-ceramic electrolytes[J]. Journal of Solid State Electrochemistry, 2013, 17: 675-680
[22] Ujiie S, Hayashi A, Tatsumisago M. Preparation and electrochemical characterization of (100-x)(0.7Li₂S·0.3P₂S₅)·xLiBr glass-ceramic electrolytes[J]. Materials Renewable and Sustainable Energy, 2013, 3(1):1-8
[23] Ujiie S, Inagaki T, Hayashi A. Conductivity of 70Li₂S-30P₂S₅ glass and glass-ceramics added with lithium halides[J]. Solid State Ionics, 2014, 263: 57-61
[24] Yamauchi A, Sakuda A, Hayashi A, et al. Preparation and ionic conductivities of (100-x)(0.75LiS·0.25P₂S₅)·LiBH₄ glass electrolytes[J]. Journal of Power Sources, 2013, 244: 707-710
[25] Liu Z Q, Tang Y F, Wang Y M, et al. High performance Li₂S-P₂S₅ solid electrolyte induced by selenide[J]. Journal of Power Sources, 2014, 260: 264-267
[26] Muramatsu H, Hayashi A, Ohtomo T, et al. Structure changes of Li₂S-P₂S₅ sulfide electrolytes in the atmosphere[J]. Solid State Ionics, 2011, 182: 116-119
[27] Ohtomo T, Hayashi A, Tatsumisago M, et al. Suppression of H₂S gas generation from 75Li₂S·25P₂S₅[J]. Journal of Materials Science, 2013, 48: 4 137-4 142
[28] Hayashi A, Muramatsu H, Ohtomo T, et al. Improvement of chemical stability of Li₃PS₄ glass electrolytes by adding M_xO_y(M=Fe, Zn, and Bi) nanoparticles[J]. Journal of Materials Chemistry A, 2013, 1: 6 320-6 326
[29] Ohtomo T, Hayashi A, Tatsumisago M, et al. Characteristics of the Li₂O-Li₂S-P₂S₅ glasses synthesized by the two-step mechanical milling[J]. Journal of Non-Crystalline Solids, 2013, 364: 57-61
[30] Hayashi A, Muramatsu H, Ohtomo T, et al. Improved chemical stability in Li₂S-P₂S₅-P₂O₅-ZnO composite electrolytes for all-solid-state rechargeable lithium batteries[J]. Journal of Alloys and Compounds, 2014, 591: 247-250
[31] Ohtomo T, Hayashi A, Tatsumisago M, et al. Glass electrolytes with high ion conductivity and high chemical stability in the system LiI-Li₂O-Li₂S-P₂O₅[J]. Electrochemistry, 2013, 81(6): 428-431
[32] Ohtomo T, Hayashi A, Tatsumisago M, et al. All-Solid-State batteries with Li₂O-Li₂S-P₂S₅ glass electrolytes synthesized by two-step mechanical milling[J]. Journal of Solid State Electrochemistry, 2013, 17: 2 551-2 557