固体电解质缺陷化学分析：晶粒体点缺陷及晶界空间电荷层

doi:10.19799/j.cnki.2095-4239.2021.0724

储能科学与技术 ›› 2022, Vol. 11 ›› Issue (3): 939-947.doi: 10.19799/j.cnki.2095-4239.2021.0724

• 储能新材料设计与先进表征专刊 • 上一篇下一篇

固体电解质缺陷化学分析：晶粒体点缺陷及晶界空间电荷层

邓诗维¹(), 吴剑芳¹(), 时拓²()

^1.湖南大学材料科学与工程学院，湖南省清洁能源材料及技术国际联合实验室，先进炭材料及应用技术湖南省重点实验室，湖南长沙 410082
^2.中国科学院微电子研究所微电子器件与集成技术重点实验室，北京 100020

收稿日期:2021-12-31 修回日期:2022-01-19 出版日期:2022-03-05 发布日期:2022-03-11
通讯作者: 吴剑芳,时拓 E-mail:a1305092829@163.com;jfwu@hnu.edu.cn;shituo@ime.ac.cn
作者简介:邓诗维（1999—），女，硕士研究生，研究方向为氧化物固体电解质，E-mail：a1305092829@163.com；

Defect chemistry analysis of solid electrolytes： Point defects in grain bulk and grain boundary space-charge layer

Shiwei DENG¹(), Jianfang WU¹(), Tuo SHI²()

^1.College of Materials Science and Engineering, Hunan Joint International Laboratory of Advanced Materials and Technology of Clean Energy, Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha 410082, Hunan, China
^2.The Key Laboratory of Microelectronics Devices and Integrated Technology, Institute of Microelectronics Chinese Academy of Sciences, Beijing 100020, China

Received:2021-12-31 Revised:2022-01-19 Online:2022-03-05 Published:2022-03-11
Contact: Jianfang WU,Tuo SHI E-mail:a1305092829@163.com;jfwu@hnu.edu.cn;shituo@ime.ac.cn

摘要/Abstract

摘要：

离子电导率是影响固态离子器件性能的基本因素。在无机固体电解质中，离子的传导包括晶粒体和晶界传导，两者均与材料体系中点缺陷结构密切相关。本文详细阐述了固体电解质体内可能存在的点缺陷及其对晶粒体电导率的影响规律，并结合钙钛矿结构LLTO固体电解质介绍了晶界空间电荷层模型及由此而引发的晶界离子电导特性。以期为高离子电导固体电解质的设计提供思路。

关键词: 固态电解质, 缺陷, 离子电导, 空间电荷层

Abstract:

The fundamental factor determining the performance of solid-state ionic devices is their ionic conductivity. Ion conduction in inorganic solid electrolytes involves migration in the grain bulk and across the grain boundary, which is correlated with the structure of the point defect. The various point defects and their influence on grain bulk conductivity are elucidated here, as well as the grain boundary space-charge layer and the derived characteristics of grain boundary conduction. The content would provide some guidance in the design of solid electrolytes with high ionic conductivity.

Key words: solid electrolyte, defects, ion conduction, space-charge layer

中图分类号:

TQ 028.8

邓诗维, 吴剑芳, 时拓. 固体电解质缺陷化学分析：晶粒体点缺陷及晶界空间电荷层[J]. 储能科学与技术, 2022, 11(3): 939-947.

Shiwei DENG, Jianfang WU, Tuo SHI. Defect chemistry analysis of solid electrolytes： Point defects in grain bulk and grain boundary space-charge layer[J]. Energy Storage Science and Technology, 2022, 11(3): 939-947.

图/表 3

参考文献 32

1	FAMPRIKIS T, CANEPA P, DAWSON J A, et al. Fundamentals of inorganic solid-state electrolytes for batteries[J]. Nature Materials, 2019, 18(12): 1278-1291.
2	STRUZIK M, GARBAYO I, PFENNINGER R, et al. A simple and fast electrochemical CO₂ sensor based on Li₇La₃Zr₂O₁₂ for environmental monitoring[J]. Advanced Materials, 2018, 30(44): doi: 10.1002/adma.201804098.
3	WEDIG A, LUEBBEN M, CHO D Y, et al. Nanoscale cation motion in TaOx, HfOx and TiOx memristive systems[J]. Nature Nanotechnology, 2016, 11(1): 67-74.
4	LIN Y, FANG S, SU D, et al. Enhancing grain boundary ionic conductivity in mixed ionic-electronic conductors[J]. Nature Communications, 2015, 6: doi: 10.1038/ncomms7824.
5	JANEK J, ZEIER W G. A solid future for battery development[J]. Nature Energy, 2016, 1: doi: 10.1038/nenergy.2016.141.
6	GAO Y R, NOLAN A M, DU P, et al. Classical and emerging characterization techniques for investigation of ion transport mechanisms in crystalline fast ionic conductors[J]. Chemical Reviews, 2020, 120(13): 5954-6008.
7	LAU J, DEBLOCK R H, BUTTS D M, et al. Sulfide solid electrolytes for lithium battery applications[J]. Advanced Energy Materials, 2018, 8(27): doi: 10.1002/aenm.201800933.
8	GAO Z H, SUN H B, FU L, et al. Promises, challenges, and recent progress of inorganic solid-state electrolytes for all-solid-state lithium batteries[J]. Advanced Materials, 2018, 30(17): doi: 10.1002/adma.201705702.
9	BACHMAN J C, MUY S, GRIMAUD A, et al. Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction[J]. Chemical Reviews, 2016, 116(1): 140-162.
10	WU J F, ZHANG R, FU Q F, et al. Inorganic solid electrolytes for all-solid-state sodium batteries: Fundamentals and strategies for battery optimization[J]. Advanced Functional Materials, 2021, 31(13): doi: 10.1002/adfm.202008165.
11	GUO X, WASER R. Electrical properties of the grain boundaries of oxygen ion conductors: Acceptor-doped zirconia and ceria[J]. Progress in Materials Science, 2006, 51(2): 151-210.
12	WU J F, GUO X. Origin of the low grain boundary conductivity in lithium ion conducting perovskites: Li₃ xLa_{0.67‍–‍} xTiO₃[J]. Physical Chemistry Chemical Physics, 2017, 19(8): 5880-5887.
13	TENHAEFF W E, RANGASAMY E, WANG Y Y, et al. Resolving the grain boundary and lattice impedance of hot-pressed Li₇La₃Zr₂O₁₂ garnet electrolytes[J]. ChemElectroChem, 2014, 1(2): 375-378.
14	KAWAI H, KUWANO J. Lithium ion conductivity of A-site deficient perovskite solid solution La_0.67- x Li₃ x TiO₃[J]. Journal of the Electrochemical Society, 1994, 141(7): L78-L79.
15	WU J F, CHEN E Y, YU Y, et al. Gallium-doped Li₇La₃Zr₂O₁₂ garnet-type electrolytes with high lithium-ion conductivity[J]. ACS Applied Materials & Interfaces, 2017, 9(2): 1542-1552.
16	WANG Q, WU J F, LU Z H, et al. Solid electrolytes: A new lithium-ion conductor LiTaSiO₅: Theoretical prediction, materials synthesis, and ionic conductivity[J]. Advanced Functional Materials, 2019, 29(37): doi: 10.1002/adfm.201904232.
17	MOON C K, LEE H J, PARK K H, et al. Vacancy-driven Na⁺ superionic conduction in new Ca-doped Na₃PS₄ for all-solid-state Na-ion batteries[J]. ACS Energy Letters, 2018, 3(10): 2504-2512.
18	THANGADURAI V, WEPPNER W. Li₆ALa₂Ta₂O₁₂(A=Sr, Ba): Novel garnet-like oxides for fast lithium ion conduction[J]. Advanced Functional Materials, 2005, 15(1): 107-112.
19	GUO X, PITHAN C, OHLY C, et al. Enhancement of p-type conductivity in nanocrystalline BaTiO₃ ceramics[J]. Applied Physics Letters, 2005, 86(8): doi: 10.1063/1.1864232.
20	CHEN C H, AMINE K. Ionic conductivity, lithium insertion and extraction of lanthanum lithium titanate[J]. Solid State Ionics, 2001, 144(1/2): 51-57.
21	KUBICEK M, WACHTER-WELZL A, RETTENWANDER D, et al. Oxygen vacancies in fast lithium-ion conducting garnets[J]. Chemistry of Materials, 2017, 29(17): 7189-7196.
22	WOLFENSTINE J, ALLEN J L, READ J, et al. Chemical stability of cubic Li₇La₃Zr₂O₁₂ with molten lithium at elevated temperature[J]. Journal of Materials Science, 2013, 48(17): 5846-5851.
23	GREGORI G, MERKLE R, MAIER J. Ion conduction and redistribution at grain boundaries in oxide systems[J]. Progress in Materials Science, 2017, 89: 252-305.
24	SASANO S, ISHIKAWA R, SÁNCHEZ-SANTOLINO G, et al. Atomistic origin of Li-ion conductivity reduction at (Li₃ xLa_2/3- x)TiO₃ grain boundary[J]. Nano Letters, 2021, 21(14): 6282-6288.
25	GUO X, ZHANG Z L. Grain size dependent grain boundary defect structure: Case of doped zirconia[J]. Acta Materialia, 2003, 51(9): 2539-2547.
26	GUO X. Can we achieve significantly higher ionic conductivity in nanostructured zirconia? [J]. Scripta Materialia, 2011, 65(2): 96-101.
27	SATA N, EBERMAN K, EBERL K, et al. Mesoscopic fast ion conduction in nanometre-scale planar heterostructures[J]. Nature, 2000, 408(6815): 946-949.
28	MAIER J. Ionic conduction in space charge regions[J]. Progress in Solid State Chemistry, 1995, 23(3): 171-263.
29	HARUYAMA J, SODEYAMA K, HAN L Y, et al. Space-charge layer effect at interface between oxide cathode and sulfide electrolyte in all-solid-state lithium-ion battery[J]. Chemistry of Materials, 2014, 26(14): 4248-4255.
30	WU J F, GUO X. Size effect in nanocrystalline lithium-ion conducting perovskite: Li_0.30La_0.57TiO₃[J]. Solid State Ionics, 2017, 310: 38-43.
31	GUO X, VASCO E, MI S B, et al. Ionic conduction in zirconia films of nanometer thickness[J]. Acta Materialia, 2005, 53(19): 5161-5166.
32	GUO X, MI S B, WASER R. Nonlinear electrical properties of grain boundaries in oxygen ion conductors: Acceptor-doped ceria[J]. Electrochemical and Solid-State Letters, 2005, 8(1): doi: 10.1149/1.1830393.

[1]	李一涛, 沈凯尔, 庞全全. 有机物辅助的硫化物电解质基固态电池[J]. 储能科学与技术, 2022, 11(6): 1902-1918.
[2]	魏超超, 余创, 吴仲楷, 彭林峰, 程时杰, 谢佳. Li₃PS₄ 固态电解质的研究进展[J]. 储能科学与技术, 2022, 11(5): 1368-1382.
[3]	熊良涛, 王继芬, 谢华清, 章学来. 空位缺陷对单层石墨烯导热特性影响的分子动力学[J]. 储能科学与技术, 2022, 11(5): 1322-1330.
[4]	许卓, 郑莉莉, 陈兵, 张涛, 常修亮, 韦守李, 戴作强. 固态电池复合电解质研究综述[J]. 储能科学与技术, 2021, 10(6): 2117-2126.
[5]	闫汶琳, 吴凡, 李泓, 陈立泉. 含硅负极在硫化物全固态电池中的应用[J]. 储能科学与技术, 2021, 10(3): 821-835.
[6]	张赛赛, 赵海雷. 石榴石型Li₇La₃Zr₂O₁₂固态锂金属电池的界面问题研究进展[J]. 储能科学与技术, 2021, 10(3): 863-871.
[7]	朱鑫鑫, 蒋伟, 万正威, 赵澍, 李泽珩, 王利光, 倪文斌, 凌敏, 梁成都. 固态锂硫电池电解质及其界面问题研究进展[J]. 储能科学与技术, 2021, 10(3): 848-862.
[8]	张鹏, 赖兴强, 沈俊荣, 张东海, 阎永恒, 张锐, 盛军, 代康伟. 固态锂电池研究及产业化进展[J]. 储能科学与技术, 2021, 10(3): 896-904.
[9]	吴勰, 周莉, 薛照明. 基于螯合B类锂盐的固态聚合物电解质的合成及其性能[J]. 储能科学与技术, 2021, 10(1): 96-103.
[10]	李茜, 郁亚娟, 张之琦, 王磊, 黄凯. 全固态锂电池的固态电解质进展与专利分析[J]. 储能科学与技术, 2021, 10(1): 77-86.
[11]	高永晟, 陈光海, 王欣然, 白莹, 吴川. 钠离子电池电解质安全性：改善策略与研究进展[J]. 储能科学与技术, 2020, 9(5): 1309-1317.
[12]	贾曼曼, 张隆. 钠离子硫化物固态电解质研究进展[J]. 储能科学与技术, 2020, 9(5): 1266-1283.
[13]	孙歌, 魏芷宣, 张馨元, 陈楠, 陈岗, 杜菲. 钠离子无机固体电解质研究进展[J]. 储能科学与技术, 2020, 9(5): 1251-1265.
[14]	高鹏, 张珊, 贲留斌, 赵文武, 刘中柱, 朱永明, 黄学杰. 铌元素在锂离子电池中的应用[J]. 储能科学与技术, 2020, 9(5): 1443-1453.
[15]	高舒, 周敏, 韩静, 过聪, 谭媛, 蒋凯, 王康丽. 钠离子电池聚合物电解质研究进展[J]. 储能科学与技术, 2020, 9(5): 1300-1308.

固体电解质缺陷化学分析：晶粒体点缺陷及晶界空间电荷层

Defect chemistry analysis of solid electrolytes： Point defects in grain bulk and grain boundary space-charge layer

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 3

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价