A Guideline to Mitigate Interfacial Degradation Processes in Solid-State Batteries Caused by Cross Diffusion

被引：8

作者：

Din, Mir Mehraj Ud ^{[1
,2
,3
]}

Ladenstein, Lukas ^{[3
]}

Ring, Joseph ^{[4
]}

Knez, Daniel ^{[5
,6
]}

Smetaczek, Stefan ^{[4
]}

Kubicek, Markus ^{[4
]}

Sadeqi-Moqadam, Mohsen ^{[1
]}

Ganschow, Steffen ^{[5
]}

Salagre, Elena ^{[7
,8
]}

Michel, Enrique G. ^{[8
]}

Lode, Stefanie ^{[9
]}

Kothleitner, Gerald ^{[5
]}

Dugulan, Iulian ^{[10
]}

Smith, Jeffrey G. ^{[11
,12
,13
]}

Limbeck, Andreas ^{[4
]}

Fleig, Juergen ^{[4
]}

Siegel, Donald J. ^{[11
,12
,13
]}

Redhammer, Guenther J. ^{[14
]}

Rettenwander, Daniel ^{[1
,2
,3
]}

机构：

[1] NTNU Norwegian Univ Sci & Technol, Dept Mat Sci & Engn, N-7034 Trondheim, Norway

[2] NTNU Norwegian Univ Sci & Technol, Christian Doppler Lab Solid State Batteries, N-7034 Trondheim, Norway

[3] Graz Univ Technol, Inst Chem & Technol Mat, A-8010 Graz, Austria

[4] TU Wien, Inst Chem Technol & Analyt, A-1060 Vienna, Austria

[5] Graz Univ Technol, Inst Electron Microscopy & Nanoanal, Graz Ctr Electron Microscopy, A-8010 Graz, Austria

[6] Leibniz Inst Kristallzuchtung, D-12489 Berlin, Germany

[7] Univ Autonoma Madrid, Fac Ciencias, Dept Fis Mat Condensada, Madrid 28049, Spain

[8] Univ Autonoma Madrid, Condensed Matter Phys Ctr IFIMAC, Madrid 28049, Spain

[9] Norwegian Univ Sci & Technol, Dept Geosci & Petr, N-7031 Trondheim, Norway

[10] Delft Univ Technol, Fundamental Aspects Mat & Energy Grp, Mekelweg 15, NL-2629 JB Delft, Netherlands

[11] Univ Michigan, Mech Engn Dept, Ann Arbor, MI 48109 USA

[12] Univ Texas Austin, Texas Mat Inst, Oden Inst Computat Engn & Sci, Walker Dept Mech Engn, Austin, TX 78712 USA

[13] Univ Texas Austin, Joint Ctr Energy Storage Res, Austin, TX 78712 USA

[14] Univ Salzburg, Dept Chem & Phys Mat, A-5020 Salzburg, Austria

来源：

ADVANCED FUNCTIONAL MATERIALS | 2023年 / 33卷 / 42期

基金：

奥地利科学基金会;

关键词：

cross diffusion; interfacial degradation; Li7La3Zr2O12; solid electrolytes; solid-state batteries; LITHIUM ION CONDUCTION; GARNET-TYPE; ELECTROLYTE; LI7LA3ZR2O12; LICOO2; PHASE;

D O I：

10.1002/adfm.202303680

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Diffusion of transition metals across the cathode-electrolyte interface is identified as a key challenge for the practical realization of solid-state batteries. This is related to the formation of highly resistive interphases impeding the charge transport across the materials. Herein, the hypothesis that formation of interphases is associated with the incorporation of Co into the Li7La3Zr2O12 lattice representing the starting point of a cascade of degradation processes is investigated. It is shown that Co incorporates into the garnet structure preferably four-fold coordinated as Co2+ or Co3+ depending on oxygen fugacity. The solubility limit of Co is determined to be around 0.16 per formula unit, whereby concentrations beyond this limit causes a cubic-to-tetragonal phase transition. Moreover, the temperature-dependent Co diffusion coefficient is determined, for example, D-700 degrees C = 9.46 x 10(-14) cm(2) s(-1) and an activation energy E-a = 1.65 eV, suggesting that detrimental cross diffusion will take place at any relevant process condition. Additionally, the optimal protective Al2O3 coating thickness for relevant temperatures is studied, which allows to create a process diagram to mitigate any degradation with a minimum compromise on electrochemical performance. This study provides a tool to optimize processing conditions toward developing high energy density solid-state batteries.

引用

页数：13

共 58 条

[1] A shortcut to garnet-type fast Li-ion conductors for all-solid state batteries [J].