Abstract
All-solid-state batteries have attracted much attention due to their improved safety and higher energy density as compared to the conventional batteries. Owing to the excellent chemical stability against lithium metal and relatively high ionic conductivity at room-temperature, garnet-type fast lithium ion conductors with three-dimensional lithium ion transport channels are promising solid electrolytes for all-solid-state batteries. In order to better understand the intrinsic lithium-ion transport mechanisms and prevent lithium dendrite formation, it is desired to investigate single-crystal solid electrolytes. In this perspective, we review several methods reported to grow single crystals of garnet-type electrolytes. Pros and cons of different growth methods are discussed. Furthermore, we introduce some case studies on electrochemical properties of garnet-type single crystals. In addition, we provide some perspectives about potential research directions of single-crystal solid electrolytes for all-solid-state batteries.
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References
Khomenko V, Raymundo-Piñero E, Béguin F. High-energy density graphite/AC capacitor in organic electrolyte. J Power Sources. 2008;177(2):643.
Xu K. Electrolytes and interphases in Li-Ion batteries and beyond. Chem Rev. 2014;114(23):11503.
Hyooma H, Hayashi K. Crystal structures of La3Li5M2O12 (M=Nb, Ta). Mater Res Bull. 1988;23(10):1399.
Mazza D. Remarks on a ternary phase in the La2O3Me2O5Li2O system (Me=Nb, Ta). Mater Lett. 1988;7(5):205.
Murugan R, Thangadurai V, Weppner W. Fast lithium ion conduction in garnet-type Li7La3Zr2O12. Angew Chem Int Ed. 2007;46(41):7778.
Cao SY, Song SB, Xiang X, Hu QH, Zhang CF, Xia ZJ, Xu Y, Zha WP, Li JY, Gonzale PM, Han YH, Chen F. Modeling, preparation, and elemental doping of Li7La3Zr2O12 garnet-type solid electrolytes: A review. J Korean Ceram Soc. 2019;56(2):111.
Song S, Sheptyakov D, Korsunsky AM, Duong HM, Lu L. High Li ion conductivity in a garnet-type solid electrolyte via unusual site occupation of the doping Ca ions. Mater Des. 2016;93:232.
Kataoka K, Nagata H, Akimoto J. Lithium-ion conducting oxide single crystal as solid electrolyte for advanced lithium battery application. Sci Rep. 2018;8(1):9965.
Cheng EJ, Sharafi A, Sakamoto J. Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte. Electrochim Acta. 2017;223:85.
Qin Z, Meng X, Xie Y, Qian D, Deng H, Mao D, Wan L, Huang YX. Fast Li-ion transport pathways via 3D continuous networks in homogeneous garnet-type electrolyte for solid-state lithium batteries. Energy Storage Mater. 2021;43:190.
Dorai A, Kuwata N, Takekawa R, Kawamura J, Kataoka K, Akimoto J. Diffusion coefficient of lithium ions in garnet-type Li6.5La3Zr1.5Ta0.5O12 single crystal probed by 7Li pulsed field gradient-NMR spectroscopy. Solid State Ion. 2018;327:18.
Swamy T, Park R, Sheldon BW, Rettenwander D, Porz L, Berendts S, Uecker R, Carter WC, Chiang YM. Lithium metal penetration induced by electrodeposition through solid electrolytes: example in single-crystal Li6La3ZrTaO12 garnet. J Electrochem Soc. 2018;165(16):A3648.
Kataoka K, Akimoto J. High ionic conductor member of garnet-type oxide Li6.5La3Zr1.5Ta0.5O12. ChemElectroChem. 2018;5(18):2551.
Porz L, Swamy T, Sheldon BW, Rettenwander D, Frömling T, Thaman HL, Berendts S, Uecker R, Carter WC, Chiang YM. Mechanism of lithium metal penetration through inorganic solid electrolytes. Adv Energy Mater. 2017;7(20):1701003.
Pietsch P, Wood V. X-ray tomography for lithium ion battery research: a practical guide. Annu Rev Mater Res. 2017;47:451.
Redhammer GJ, Meven M, Ganschow S, Tippelt G, Rettenwander D. Single-crystal neutron and X-ray diffraction study of garnet-type solid-state electrolyte Li6La3ZrTaO12: an in situ temperature-dependence investigation (2.5 ≤ T ≤ 873 K). Acta Crystallogr Sect B Struct Sci Cryst Eng Mater. 2021;77(1):123.
Awaka J, Kijima N, Hayakawa H, Akimoto J. Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure. J Solid State Chem. 2009;182(8):2046.
Kataoka K, Akimoto J. Lithium-ion conductivity and crystal structure of garnet-type solid electrolyte Li7-xLa3Zr2-xTaxO12 using single-crystal. J Ceram Soc Jpn. 2019;127(8):521.
Xiao X, Wagata H, Hayashi F, Onodera H, Yubuta K, Zettsu N, Oishi S, Teshima K. Unique growth manner of Li5La3Ta2O12 crystals from lithium hydroxide flux at low temperature. Cryst Growth Des. 2015;15(10):4863.
Schmehr JL, Wilson SD. Active crystal growth techniques for quantum materials. Annu Rev Mater Res. 2017;47(1):153.
Paglione J, Butch NP, Rodriguez EE. Fundamentals of quantum materials: a practical guide to synthesis and exploration. New Jersey: World Scientific; 2021;83.
Matsuda Y, Itami Y, Hayamizu K, Ishigaki T, Matsui M, Takeda Y, Yamamotoa O, Imanishia N. Phase relation, structure and ionic conductivity of Li7−x−3yAlyLa3Zr2−xTaxO12. RSC Adv. 2016;6(81):78210.
Wagner R, Redhammer GJ, Rettenwander D, Senyshyn A, Schmidt W, Wilkening M, Amthauer G. Crystal structure of garnet-related Li-ion conductor Li7–3xGaxLa3Zr2O12: fast Li-ion conduction caused by a different cubic modification? Chem Mater. 2016;28(6):1861.
Hayamizu K, Terada Y, Kataoka K, Akimoto J. Toward understanding the anomalous Li diffusion in inorganic solid electrolytes by studying a single-crystal garnet of LLZO–Ta by pulsed-gradient spin-echo nuclear magnetic resonance spectroscopy. J Chem Phys. 2019;150(19):194502.
Stanje B, Rettenwander D, Breuer S, Uitz M, Berendts S, Lerch M, Uecker R, Redhammer G, Hanzu I, Wilkening M. Solid electrolytes: extremely fast charge carriers in garnet-type Li6La3ZrTaO12 single crystals. Ann Phys. 2017;529(12):1700140.
Monroe C, Newman J. The effect of interfacial deformation on electrodeposition kinetics. J Electrochem Soc. 2004;151(6):A880.
Wang C, Fu K, Kammampata SP, McOwen DW, Samson AJ, Zhang L, Hitz GT, Nolan AM, Wachsman ED, Mo YF, Thangadurai V, Hu LB. Garnet-type solid-state electrolytes: Materials, interfaces, and batteries. Chem Rev. 2020;120(10):4257.
Hongahally Basappa R, Ito T, Morimura T, Bekarevich R, Mitsuishi K, Yamada H. Grain boundary modification to suppress lithium penetration through garnet-type solid electrolyte. J Power Sources. 2017;363:145.
Li YT, Chen X, Dolocan A, Cui ZM, Xin S, Xue LG, Xu HH, Park K, Goodenough JB. Garnet electrolyte with an ultralow interfacial resistance for Li-Metal batteries. J Am Chem Soc. 2018;140(20):6448.
Dai J, Yang C, Wang C, Pastel G, Hu L. Interface engineering for garnet-based solid-state lithium-metal batteries: Materials, structures, and characterization. Adv Mater. 2018;30(48):1802068.
Wang AN, Nonemacher JF, Yan G, Finsterbusch M, Malzbender J, Krüger M. Mechanical properties of the solid electrolyte Al-substituted Li7La3Zr2O12 (LLZO) by utilizing micro-pillar indentation splitting test. J Eur Ceram Soc. 2018;38(9):3201.
Cheng Z, Zahiri B, Ji X, Chen C, Chalise D, Braun PV, Cahill DG. Good solid-state electrolytes have low, glass-like thermal conductivity. Small. 2021;17(28):2101693.
Acknowledgements
This work was supported by the start-up funds from the University of California, Riverside. The authors thank Dr. Yutao Li from the University of Texas at Austin for helpful discussion.
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Wang, YT., Chen, X. Single crystal growth and electrochemical studies of garnet-type fast Li-ion conductors. Tungsten 4, 263–268 (2022). https://doi.org/10.1007/s42864-022-00176-z
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DOI: https://doi.org/10.1007/s42864-022-00176-z