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

doi:10.19799/j.cnki.2095-4239.2021.0724

Abstract

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

CLC Number:

TQ 028.8

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.

Figures/Tables 3

References 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]	Chaochao WEI, Chuang YU, Zhongkai WU, Linfeng PENG, Shijie CHENG, Jia XIE. Research progress of Li₃PS₄ solid electrolyte [J]. Energy Storage Science and Technology, 2022, 11(5): 1368-1382.
[2]	Suting WENG, Zepeng LIU, Gaojing YANG, Simeng ZHANG, Xiao ZHANG, Qiu FANG, Yejing LI, Zhaoxiang WANG, Xuefeng WANG, Liquan CHEN. Cryogenic electron microscopy （cryo-EM） characterizing beam-sensitive materials in lithium metal batteries [J]. Energy Storage Science and Technology, 2022, 11(3): 760-780.
[3]	Dangling LIU, Shimin WANG, Zhihui GAO, Lufu XU, Shubiao XIA, Hong GUO. Properties of three-dimensional NZSPO/PAN-［PEO-NATFST］ sodium-battery-composite solid electrolyte [J]. Energy Storage Science and Technology, 2021, 10(3): 931-937.
[4]	Saisai ZHANG, Hailei ZHAO. Electrode/electrolyte interfaces in Li₇La₃Zr₂O₁₂ garnet-based solid-state lithium metal battery： Challenges and progress [J]. Energy Storage Science and Technology, 2021, 10(3): 863-871.
[5]	Yanming CUI, Zhihua ZHANG, Yuanqiao HUANG, Jiu LIN, Xiayin YAO, Xiaoxiong XU. Prototype all-solid-state battery electrodes preparation and assembly technology [J]. Energy Storage Science and Technology, 2021, 10(3): 836-847.
[6]	Peng ZHANG, Xingqiang LAI, Junrong SHEN, Donghai ZHANG, Yongheng YAN, Rui ZHANG, Jun SHENG, Kangwei DAI. Research and industrialization progress of solid-state lithium battery [J]. Energy Storage Science and Technology, 2021, 10(3): 896-904.
[7]	Xi LI, Yajuan YU, Zhiqi ZHANG, Lei WANG, Kai HUANG. Advance and patent analysis of solid electrolyte in solid-state lithium batteries [J]. Energy Storage Science and Technology, 2021, 10(1): 77-86.
[8]	Manman JIA, Long ZHANG. Recent development on sulfide solid electrolytes for solid-state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1266-1283.
[9]	Ge SUN, Zhixuan WEI, Xinyuan ZHANG, Nan CHEN, Gang CHEN, Fei DU. Recent progress of sodium-based inorganic solid electrolytes [J]. Energy Storage Science and Technology, 2020, 9(5): 1251-1265.
[10]	Peng GAO, Shan ZHANG, Liubin BEN, Wenwu ZHAO, Zhongzhu LIU, Rogerio RIBAS, Yongming ZHU, Xuejie HUANG. Application of niobium in lithium ion batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1443-1453.
[11]	Shu GAO, Min ZHOU, Jing HAN, Cong GUO, Yuan TAN, Kai JIANG, Kangli WANG. Progress on polymer electrolyte in sodium ion batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1300-1308.
[12]	Jie WU, Xiaobiao JIANG, Yang YANG, Yongmin WU, Lei ZHU, Weiping TANG. Progress of NASICON-structured Li₁₊_xAl_xTi₂_-_x(PO₄)₃(0 ≤x≤ 0.5) solid electrolyte [J]. Energy Storage Science and Technology, 2020, 9(5): 1472-1488.
[13]	Jing YANG, Gaozhan LIU, Lin SHEN, Xiayin YAO. Research progress on NASICON-structured sodium solid electrolytes and their derived solid state sodium batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1284-1299.
[14]	Linfeng PENG, Huanhuan JIA, Qing DING, Yuming ZHAO, Jia XIE, Shijie CHENG. Research progress of solid-state sodium batteries using inorganic sodium ion conductors [J]. Energy Storage Science and Technology, 2020, 9(5): 1370-1382.
[15]	Mengying MA, Huilin PAN, Yongsheng HU. Progress in electrolyte research for non-aqueous sodium ion batteries [J]. Energy Storage Science and Technology, 2020, 9(5): 1234-1250.