张楠,钟学奇,丁飞,赵旭升,刘兴江,徐强

• 1:天津大学化工学院
• 2:中国电子科技集团公司第十八研究所物理与化学电源国防重点实验室
• 3:青海民族大学化学化工学院

摘要(Abstract)：

为了提高70Li_2S-30P_2S_5玻璃陶瓷态电解质的离子电导率和电化学性能,提出利用Ce_2S_3掺杂改性的方法。采用高能球磨和热处理相结合的方法制备了一系列组分为70Li_2S-(30-x)P_2S_5-xCe_2S_3 (x=0, 0.5, 1, 2, 3)的玻璃陶瓷态电解质。通过差示扫描量热法(DSC),X射线衍射(XRD),拉曼光谱,扫描电子显微镜(SEM)和电化学测试等表征手段,对掺杂不同比例Ce_2S_3的Li_2S-P_2S_5基固体电解质进行分析测试。研究结果表明:掺杂适量的Ce_2S_3不仅可以提高70Li_2S-30P_2S_5玻璃陶瓷态电解质的离子电导率,还可以降低其与正极材料的界面电阻。其中,掺杂1%Ce_2S_3得到的70Li_2S-29P_2S_5-1Ce_2S_3玻璃陶瓷态电解质表现出最高的室温离子电导率(1.52×10~(-3)S×cm~(-1)),明显高于70Li_2S-30P_2S_5玻璃陶瓷态电解质的室温离子电导率。对比LiCoO_2/70Li_2S-30P_2S_5/Li-In和LiCoO_2/70Li_2S-29P_2S_5-1Ce_2S_3/Li-In2种全固态锂电池,后者表现出更好的放电性能,在室温下0.1C时的初始放电比容量为105.3 mAh×g~(-1),循环50圈后的放电比容量为91.8 mAh×g~(-1),容量保持率为87.2%。

关键词(KeyWords)： 掺杂;三硫化二铈;硫化物固体电解质;离子电导率;全固态锂电池

Abstract:

Keywords:

基金项目(Foundation): 天津市自然科学基金(17JCYBJC20900)

作者(Author): 张楠,钟学奇,丁飞,赵旭升,刘兴江,徐强

参考文献(References)：

• [1]李泓,许晓雄.固态锂电池研发愿景和策略[J].储能科学与技术, 2016, 5(5):607-614.LI H, XU X X. R&D vision and strategies on solid lithium batteries[J]. Energy Storage Science and Technology, 2016, 5(5):607-614.
• [2] FAN L, WEI S Y, LI S Y, et al. Recent progress of the solid-state electrolytes for high-energy metal-based batteries[J]. Advanced Energy Materials, 2018, 8(11):1-31.
• [3] CHEN R J, QU W J, GUO X, et al. The pursuit of solid-state electrolytes for lithium batteries:from comprehensive insight to emerging horizons[J]. Materials Horizons, 2016, 3(6):487-516.
• [4] CHEN S, XIE D, LIU G, et al. Sulfide solid electrolytes for all-solid-state lithium batteries:Structure, conductivity, stability and application[J]. Energy Storage Materials, 2018, 14:58-74.
• [5] PARK KERN H, BAI Q, KIM DONG H, et al. Design strategies, practical considerations, and new solution processes of sulfide solid electrolytes for all-solid-state batteries[J]. Advanced Energy Materials, 2018, 8(18):1-24.
• [6] KAMAYA N, HOMMA K, YAMAKAWA Y, et al. A lithium superionic conductor[J]. Nature Materials, 2011, 10(9):682-686.
• [7] MA Z, XUE H G, GUO S P. Recent achievements on sulfide-type solid electrolytes:Crystal structures and electrochemical performance[J]. Journal of Materials Science, 2018, 53(6):3927-3938.
• [8] BUSCHE M R, WEBER D A, SCHNEIDER Y, et al. In situ monitoring of fast Li-ion conductor Li7P3S11 crystallization inside a hot-press setup[J]. Chemistry of Materials, 2016, 28(17):6152-6165.
• [9] CHU I H, NGUYEN H, HY S, et al. Insights into the performance limits of the Li7P3S11 superionic conductor:a combined first-principles and experimental study[J]. Acs Applied Materials&Interfaces, 2016, 8(12):7843-7853.
• [10] MCGROGAN F P, SWAMY T, BISHOP S R, et al. Compliant yet brittle mechanical behavior of Li2S-P2S5 lithium-ion-conducting solid electrolyte[J]. Advanced Energy Materials, 2017, 7(12):1-5.
• [11] ZHANG Y B, CHEN R J, LIU T, et al. High capacity, superior cyclic performances in all-solid-state lithium-ion batteries based on78Li2S-22P2S5 glass-ceramic electrolytes prepared via simple heat treatment[J]. Acs Applied Materials&Interfaces, 2017, 9(34):28542-28548.
• [12] ZHANG Y B, CHEN K, SHEN Y, et al. Synergistic effect of processing and composition x on conductivity of xLi2S-(100-x)P2S5electrolytes[J]. Solid State Ionics, 2017, 305:1-6.
• [13] SEINO Y, OTA T, TAKADA K, et al. A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries[J]. Energy&Environmental Science, 2014, 7(2):627-631.
• [14] HUANG B X, YAO X Y, HUANG Z, et al. Li3PO4-doped Li7P3S11 glass-ceramic electrolytes with enhanced lithium ion conductivities and application in all-solid-state batteries[J]. Journal of Power Sources, 2015, 284:206-211.
• [15] LU P H, DING F, XU Z B, et al. Study on(100-x)(70Li2S-30P2S5)-xLi2ZrO3 glass-ceramic electrolyte for all-solid-state lithium-ion batteries[J]. Journal of Power Sources, 2017, 356:163-171.
• [16] FUKUSHIMA A, HAYASHI A, YAMAMURA H, et al. Mechanochemical synthesis of high lithium ion conducting solid electrolytes in a Li2S-P2S5-Li3N system[J]. Solid State Ionics, 2017, 304:85-89.
• [17] UJIIE S, INAGAKI T, HAYASHI A, et al. Conductivity of 70Li2S-30P2S5 glasses and glass-ceramics added with lithium halides[J].Solid State Ionics, 2014, 263:57-61.
• [18] TAO Y C, CHEN S J, LIU D, et al. Lithium superionic conducting oxysulfide solid electrolyte with excellent stability against lithium metal for all-solid-state cells[J]. Journal of the Electrochemical Society, 2016, 163(2):A96-A101.
• [19] XIE D J, CHEN S J, ZHANG Z H, et al. High ion conductive Sb2O5-dopedβ-Li3PS4 with excellent stability against Li for all-solid-state lithium batteries[J]. Journal of Power Sources, 2018, 389:140-147.
• [20] LIU G, XIE D, WANG X, et al. High air-stability and superior lithium ion conduction of Li3+3xP1-xZnxS4-xOx by aliovalent substitution of ZnO for all-solid-state lithium batteries[J]. Energy Storage Materials, 2018, 17:266-274.
• [21] XU R C, XIA X H, WANG X L, et al. Tailored Li2S-P2S5 glass-ceramic electrolyte by MoS2 doping, possessing high ionic conductivity for all-solid-state lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2017, 5(6):2829-2834.
• [22]陈昆峰,李宫,梁晰童,等.稀土改性电化学储能电极材料的研究进展[J].硅酸盐学报, 2016, 44(8):1241-1247.CHEN K F, LI G, LIANG X T, et al. Rare earth element ion modified electrochemical energy storage electrode materials–ashort review[J]. Journal of the Chinese Ceramic Society, 2016, 44(8):1241-1247.
• [23] PARK M, JUNG H G, JUNG W D, et al. Chemically evolved composite lithium-ion conductors with lithium thiophosphates and nickel sulfides[J]. Acs Energy Letters, 2017, 2(8):1740-1745.
• [24] XU R C, XIA X H, LI S H, et al. All-solid-state lithium-sulfur batteries based on a newly designed Li7P2.9Mn0.1S10.7I0.3 superionic conductor[J]. Journal of Materials Chemistry A, 2017, 5(13):6310-6317.
• [25]陈骋,凌仕刚,郭向欣,等.-固态锂二次电池关键材料中的空间电荷层效应:原理和展望[J].储能科学与技术, 2016, 5(5):668-677.CHEN C, LING S G, GUO X X, et al. Space charge layer effect in rechargeable solid state lithium batteries:Principle and perspective[J]. Energy Storage Science and Technology, 2016, 5(5):668-677.