Characterization and testing of key electrical and electrochemical properties of lithium-ion solid electrolytes

doi:10.19799/j.cnki.2095-4239.2019.0296

Abstract

Abstract:

Lithium-ion solid electrolyte is a key material for the development of high-safety solid-state lithium batteries, and its electrochemical performance is closely related to the full batteries. Ionic conductivity, electronic conductivity, electrochemical window, and stability versus lithium interface are the key electrical and electrochemical properties of solid electrolytes. In-depth characterization and analysis can help understand the compatibility between different electrolyte and electrode materials, which facilitates the development of high-performance solid-state lithium batteries. This study introduces different types of lithium-ion solid electrolytes. The key electrochemical performances, methods, principles, and equipment for testing are described. In addition, the analysis of the data is described in combination with specific cases.

Key words: solid electrolytes, conductivity, electrochemical window, interfacial stability, lithium batteries

CLC Number:

TM 911

HUANG Xiao, WU Linbin, HUANG Zhen, LIN Jiu, XU Xiaoxiong. Characterization and testing of key electrical and electrochemical properties of lithium-ion solid electrolytes[J]. Energy Storage Science and Technology, 2020, 9(2): 479-500.

Figures/Tables 9

References 44

1	Torben APP , Steen SKAARUP , Alan HOOPER . Ionic conductivity of pure and doped Li₃N[J]. Solid State Ionics, 1983, 11(2): 97-103.
2	KHORASSANI A , IZQUIERDO G , WEST A R . The solid electrolyte system, Li₃PO₄-Li₄SiO₄ [J]. Materials Research Bulletin, 1981, 16(12): 1561-1567.
3	ANDREEV O L , ZELYUTIN G V , MARTEM'YANOVA Z S , et al . Electrical conductivity of Li₆BeO₄-Li₅AlO₄ solid solutions[J]. Inorganic Materials, 2001, 37(2): 177-179.
4	HONG H Y P . Crystal structure and ionic conductivity of Li₁₄Zn(GeO₄)₄ and other new Li⁺ superionic conductors[J]. Materials Research Bulletin, 1978, 13(2): 117-124.
5	Leif NILSSON , Hessel ANDERSENN , Arnold LUNDéN . The structure of the solid electrolyte LiAgSO₄ at 803 K and of LiNaSO₄ at 848 K[J]. Solid State Ionics, 1989, 34(1-2): 111-119.
6	Roy TÄRNEBERG , Arnold LUND . Ion diffusion in the high-temperature phases Li₂SO₄, LiNaSO₄, LiAgSO₄ and Li₄Zn(SO₄)₃ [J]. Solid State Ionics, 1996, 90(1-4): 209-220.
7	LI Xiaona , LIANG Jianwen , LUO Jing , et al . Air-stable Li₃InCl₆ electrolyte with high voltage compatibility for all-solid-state batteries[J]. Energy & Environmental Science, 2019, 12(9): 2665-2671.
8	Koji YAMADA , Keiji KUMANO , Tsutomu OKUDA . Lithium superionic conductors Li₃InBr₆ and LiInBr₄studied by ⁷Li, ¹¹⁵In NMR[J]. Solid State Ionics, 2006, 177(19-25): 1691-1695.
9	HUA Chunxiu , FANG Xiangpeng , WANG Zhaoxiang , et al . Lithium storage in perovskite lithium lanthanum titanate[J]. Electrochemistry Communications, 2013, 32: 5-8.
10	Alexandra EMLY , Emmanouil KIOUPAKIS , Anton VAN DER VEN . Phase stability and transport mechanisms in antiperovskite Li₃OCl and Li₃OBr superionic conductors[J]. Chemistry of Materials, 2013, 25(23): 4663-4670.
11	Venkataraman THANGADURAI , SHUKLA Ashok K , Jagannatha GOPALA-KRISHNAN . New lithium-ion conductors based on the NASICON structure[J]. Journal of Materials Chemistry, 1999, 9(3): 739-741.
12	MURUGAN R , THANGADURAI V , WEPPNER W . Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂ [J]. Angewandte Chemie-International Edition, 2007, 46(41): 7778-7781.
13	RAMAKUMAR S , DEVIANNAPOORANI C , DHIVYA L , et al . Lithium garnets: Synthesis, structure, Li⁺ conductivity, Li⁺ dynamics and applications[J]. Progress in Materials Science, 2017, 88: 325-411.
14	AkitoshiI HAYASH , Shigenori HAMA , Hideyuki MORIMOTO , et al . Preparation of Li₂S-P₂S₅ amorphous solid electrolytes by mechanical milling[J]. Journal of the American Ceramic Society, 2001, 84(2): 477-479.
15	Kenji HOMMA , Masao YONEMURA , Takeshi KOBAYASHI , et al . Crystal structure and phase transitions of the lithium ionic conductor Li₃PS₄ [J]. Solid State Ionics, 2011, 182(1): 53-58.
16	Hisanori YAMANE , Masatoshi SHIBATA , Yukio SHIMANE , et al . Crystal structure of a superionic conductor, Li₇P₃S₁₁ [J]. Solid State Ionics, 2007, 178(15-18): 1163-1167.
17	Ezhiylmurugan RANGASAMY , LIU Zengcai , Mallory GOBET , et al . An iodide-based Li₇P₂S₈I superionic conductor[J]. Journal of the American Chemical Society, 2015, 137(4): 1384-1387.
18	Ryoji KANNO , Masahiro MURAYAMA . Lithium ionic conductor thio-LISICON: The Li₂S-GeS₂-P₂S₅ system[J]. Journal of the Electrochemical Society, 2001, 148(7): A742-A746.
19	Noriaki KAMAYA , Kenji HOMMA , Yuichiro YAMAKAWA , et al . A lithium superionic conductor[J]. Nature Materials, 2011, 10(9): 682-686.
20	HORI S , KATO M , SUZUKI K , et al . Phase diagramof the Li₄GeS₄-Li₃PS₄ quasi-binary system containing the superionic conductor Li₁₀GeP₂S₁₂ [J]. Journal of the American Ceramic Society, 2015, 98(10): 3352-3360.
21	Yuki KATO , Satoshi HORI , Toshiya SAITO , et al . High-power all-solid-state batteries using sulfide superionic conductors[J]. Nature Energy, 2016, 1(4):doi: 10.1038/nenergy.2016.30.
22	Hans-Joerg DEISEROTH , KONG Shiao Tong , Hellmut ECKERT , et al . Li₆PS₅X: A class of crystalline Li-rich solids with an unusually high Li⁺ mobility[J]. Angewandte Chemie-International Edition, 2008, 47(4): 755-758.
23	RAO R P , SHARMA N , PETERSON V K , et al . Formation and conductivity studies of lithium argyrodite solid electrolytes using in-situ neutron diffraction[J]. Solid State Ionics, 2013, 230: 72-76.
24	ADELI P , BAZAK J D , PARK K H , et al . Boosting solid-state diffusivity and conductivity in lithium superionic argyrodites by halide substitution[J]. Angewandte Chemie International Edition, 2019, 58(26): 8681-8686.
25	LIU Jun , BAO Zhenan , CUI Yi , et al . Pathways for practical high-energy long-cycling lithium metal batteries[J]. Nature Energy, 2019, 4(3): 180-186.
26	HODGE I M , INGRAM M D , WEST A R . Impedance and modulus spectroscopy of polycrystalline solid electrolytes[J]. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1976, 74(2): 125-143.
27	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.
28	REN Yaoyu , CHEN Kai , CHEN Rujun , et al . Oxide electrolytes for lithium batteries[J]. Journal of the American Ceramic Society, 2015, 98(12): 3603-3623.
29	BI Jiaying , MU Daobin , WU Borong , et al . A hybrid solid electrolyte Li_0.33La_0.557TiO₃/poly(acylonitrile) membrane infiltrated with a succinonitrile-based electrolyte for solid state lithium-ion batteries[J]. Journal of Materials Chemistry A, 2020, doi: 10.1039/C9TA08601C . doi: 10.1039/C9TA08601C
30	CHEN Shaojie , XIE Dongjiu , LIU Gaozhan , et al . Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application[J]. Energy Storage Materials, 2018, 14: 58-74.
31	ZHANG Qingqing , LIU Kai , DING Fei , et al . Recent advances in solid polymer electrolytes for lithium batteries[J]. Nano Research, 2017, 10(12): 4139-4174.
32	CHENG Xunliang , PAN Jian , ZHAO Yang , et al . Gel polymer electrolytes for electrochemical energy storage[J]. Advanced Energy Materials, 2018, 8(7): doi: 10.1002/aenm.201702184.
33	RIESS I . Review of the limitation of the Hebb-Wagner polarization method for measuring partial conductivities in mixed ionic electronic conductors[J]. Solid State Ionics, 1996, 91(3/4): 221-232.
34	KVAN BEEK L . AC and DC polarization effects in a protonic conductor (borax)[J]. Physica, 1963, 29(3): 215-224.
35	Jun-ichiro MIZUSAKI , Kazuo FUEKI , Takashi MUKAIBO . An investigation of the Hebb-Wagner’s dc polarization technique I. Steady-state chemical potential profiles in solid electrolytes[J]. Bulletin of the Chemical Society of Japan, 1975, 48(2): 428-431.
36	HAN F D , ZHU Y Z , HE X F , et al . Electrochemical stability of Li₁₀GeP₂S₁₂ and Li₇La₃Zr₂O₁₂ solid electrolytes[J]. Advanced Energy Materials, 2016, 6(8): doi: 10.1002/aenm.201501590.
37	WANG Yuxing , LU Dongping , XIAO Jie , et al . Superionic conduction and interfacial properties of the low temperature phase Li₇P₂S₈Br_0.5I_0.5 [J]. Energy Storage Materials, 2019, 19: 80-87.
38	DUAN Huanan , ZHENG Hongpeng , ZHOU Ying , et al . Stability of garnet-type Li ion conductors: An overview[J]. Solid State Ionics, 2018, 318: 45-53.
39	LU Yang , HUANG Xiao , SONG Zhen , et al . Highly stable garnet solid electrolyte based Li-S battery with modified anodic and cathodic interfaces[J]. Energy Storage Materials, 2018, 15: 282-290.
40	Kazunori TAKADA , Narumi OHTA , ZHANG Lianqi , et al . Interfacial phenomena in solid-state lithium battery with sulfide solid electrolyte[J]. Solid State Ionics, 2012, 225: 594-597.
41	ZHANG Z H , CHEN S J , YANG J , et al . Interface re-engineering of Li₁₀GeP₂S₁₂ electrolyte and lithium anode for all-solid-state lithium batteries with ultralong cycle life[J]. ACS Applied Materials & Interfaces, 2018, 10(3): 2556-2565.
42	LU Yang , HUANG Xiao , RUAN Yadong , et al . An in-situ element permeation constructed high endurance Li-LLZO interface at high current densities[J]. Journal of Materials Chemistry A, 2018, 6(39): 18853-18858.
43	HUANG Xiao , LU Yang , SONG Zhen , et al . Manipulating Li₂O atmosphere for sintering dense Li₇La₃Zr₂O₁₂ solid electrolyte[J]. Energy Storage Materials, 2019, 22: 207-217.
44	HUANG Xiao , LU Yang , GUO Haojie , et al . None-mother-powder method to prepare dense Li-garnet solid electrolytes with high critical current density[J]. ACS Applied Energy Materials, 2018, 1(10): 5355-5365.

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