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Garnet-type solid-state electrolytes: crystal structure, interfacial challenges and controlling strategies

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Abstract

All-solid-state batteries (ASSBs) hold great promise for next-generation energy storage technologies owing to their advantage in different aspects such as energy density, safety, and wide temperature tolerance. However, the use of solid-state electrolytes (SSEs) instead of liquid ones meanwhile brings serious concerns related to the point-to-point contact between SSEs and electrodes, which is known to result in high interface resistance and inhomogeneous distribution of charges during the Li+ plating/stripping process, eventually leading to a premature failure of ASSBs. This review focuses on the garnet-type SSEs in the formula of Li7La3Zr2O12 (LLZO), and discusses the structure-performance relationship of this ceramic electrolyte in detail to achieve a clear understanding of its Li+ transmission mechanism. Meanwhile, the challenges of cubic phase LLZO (c-LLZO) for their application in solid-state batteries (SSBs) are demonstrated by the Li/LLZO interface, which features the importance of Li metal wettability and dendrite suppression for sustainable performance. Furthermore, this review summarizes the recent research strategies to combat these contact issues at the Li/LLZO interface, highlighting the essential role played by surface modification of LLZO electrolytes. Following the obtained insights, perspectives for future research on LLZO to accelerate its potential development of SSBs in commercialized applications are also provided.

Graphical Abstract

摘要

全固态电池（ASSBs）因其在能量密度、安全性和比较宽的温度工作范围等方面的优势，被认为是下一代储能技术的发展方向。然而，使用固态电解质代替液体电解质可能会带来其他相关的问题，比如固态电解质和电极之间的点对点接触，已知该不良接触会导致高界面电阻和Li+电镀/剥离过程中不均匀的电荷分布，进而最终导致ASSBs的过早失效。在我们的综述中，我们以公式为Li7La3Zr2O12 (LLZO)的石榴石型固态电解质为研究对象，详细讨论了这种陶瓷电解质的结构-性能关系，以明确其Li+传输机制。同时，以Li/LLZO界面为例介绍了立方相-LLZO在固态电池应用中面临的界面挑战，突出了Li金属润湿性和锂枝晶的抑制能力对可持续性能的重要性。此外，本综述还总结了解决Li/LLZO界面接触问题的最新研究策略，强调了LLZO电解质表面改性的重要作用。根据获得的见解，我们还对LLZO的未来研究提出了展望，以加速其在SSBs商业化应用中的发展。

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Fig. 1

Reproduced with permission from Ref. [21]. Copyright 2009, Elsevier. b Cubic phase of LLZO. Reproduced with permission from Ref. [22]. Copyright 2011, Chemical Society Japan. Loop structures of Li+ migration pathway of c t-LLZO and d c-LLZO, where g stands for site occupancy ratio

Fig. 2

Reproduced with permission from Ref. [28]. Copyright 2015, American Chemical Society

Fig. 3

Reproduced with permission from Ref. [71]. Copyright 2022, John Wiley and Sons. b Lithium dendrites growth. Reproduced with permission from Ref. [72]. Copyright 2020, American Chemical Society

Fig. 4

Reproduced with permission from Ref. [73]. Copyright 2017, American Chemical Society. b Surface chemistry of LLZO exposed to humid air. Reproduced with permission from Ref. [74]. Copyright 2017 Royal Society of Chemistry. c Contact angle of molten Li on Li2CO3. Reproduced with permission from Ref. [73]. Copyright 2017, American Chemical Society. d SEM image of metallic Li/LLZO interface. Reproduced with permission from Ref. [75]. Copyright 2019, American Chemical Society

Fig. 5

Reproduced with permission from Ref. [79]. Copyright 2018, American Chemical Society. b Interconnected holes (SE stands for second electron; BSE stands for backscattered electron). Reproduced with permission from Ref. [82]. Copyright 2015, Elsevier. c Cracks and d drain boundaries. Reproduced with permission from Ref. [83]. Copyright 2016, Elsevier

Fig. 6

Reproduced with permission from Ref. [89]. Copyright 2014, the Royal Society of Chemistry. b Sintering LLZT after introducing C. Reproduced with permission from Ref. [91]. Copyright 2018, American Chemical Society. c Immediate processing of LLZO surfaces with HCl solution. Reproduced with permission from Ref. [92]. Copyright 2019, Elsevier. d Immediate processing of LLZO surfaces with H3PO4 solution. Reproduced with permission from Ref. [93]. Copyright 2019, The Royal Society of Chemistry

Fig. 7

Reproduced with permission from Ref. [94]. Copyright 2017, American Association for the Advancement of Science. b Schematic diagram of wetting behavior of garnet-type SSEs surface by molten Li after adding Al2O3; c electrochemical impedance spectroscopy (EIS) profiles of Li/Al2O3-coated LLZO/Li and Li/LLZO/Li. Reproduced with permission from Ref. [100]. Copyright 2018, Springer Nature. d Drawing a graphite-based soft interface on LLZWO surface; e wettability comparison of Li on Li5.9Al0.2La3Zr1.75W0.25O12 (LLZWO) with and without graphite-based soft interface coating; f wetting behaviors of Li on graphite-coated LLZO. Reproduced with permission from Ref. [107]. Copyright 2018, American Chemical Society. g Schematic illustration of CAD method (PAA stands for poly(acrylic acid)); h SEM image of Li/LLZO interface after having an ultra-stable cycle capacity for 1000 h. Reproduced with permission from Ref. [108]. Copyright 2022, American Chemical Society. i Schematic illustration of in-situ surface modification of LLZTO by metal salt solution. Reproduced with permission from Ref. [112]. Copyright 2019, American Chemical Society. j Schematic diagram of LLZTO surface state before and after NH4F treatment. Reproduced with permission from Ref. [116]. Copyright 2020, John Wiley and Sons

Fig. 8

Reproduced with permission from Ref. [121]. Copyright 2017, American Chemical Society. d Schematic diagram of interface by introducing glue adhesiveness; e SEM images of cross-section of cathode/cured glue/anode cell; f voltage profiles of Li symmetrical cells with/without glue. Reproduced with permission from Ref. [122]. Copyright 2019, American Chemical Society

Fig. 9

Reproduced with permission from Ref. [126]. Copyright 2019, John Wiley and Sons. c Schematic diagram of interface contact between Li/LLZO and Li–C3N4/LLZO; d CCD curve of Li–C3N4/LLZO/Li–C3N4 symmetric cells. Reproduced with permission from Ref. [127]. Copyright 2020, John Wiley and Sons

Fig. 10

Reproduced with permission from Ref. [131]. Copyright 2020, American Chemical Society

Fig. 11

Reproduced with permission from Ref. [133]. Copyright 2018, American Chemical Society. b Li/3D-SSE/Li battery manufacturing process diagram. Reproduced with permission from Ref. [134]. Copyright 2021, John Wiley and Sons

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22025507 and 21931012), the Key Research Program of Frontier Sciences, CAS (No. ZDBS-LY-SLH020), Beijing National Laboratory for Molecular Sciences (No. BNLMS-CXXM-202010).

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Authors and Affiliations

  1. National Engineering Research Center for Advanced Polymer Processing Technology, Key Laboratory of Advanced Material Processing & Mold (Ministry of Education), Zhengzhou University, Zhengzhou, 450002, China

    Ting-Ting Wu, Chang-Yu Shen & Xian-Hu Liu

  2. CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing, 100190, China

    Ting-Ting Wu, Sijie Guo, Bing Li & An-Min Cao

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Bing Li & An-Min Cao

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Wu, TT., Guo, S., Li, B. et al. Garnet-type solid-state electrolytes: crystal structure, interfacial challenges and controlling strategies. Rare Met. 42, 3177–3200 (2023). https://doi.org/10.1007/s12598-023-02323-y

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