石榴石型固态电解质Li7La3Zr2O12的改性研究现状

摘要/Abstract

摘要： 固态电解质是高安全性、高能量密度的全固态锂电池的核心部件,其典型代表Li₇La₃Zr₂O₁₂(LLZO)具有高离子电导率、高机械强度、高电化学稳定性、低界面阻抗以及对锂金属负极良好的稳定性等优势,是科研人员重点关注的对象之一,但与液态电解质相比,目前LLZO仍存在低离子电导率和与电极固-固界面接触等问题。本文主要简介了LLZO的晶体结构、改性方式等对其离子电导率及界面阻抗的影响,同时对LLZO现存的问题进行了总结,对LLZO的未来发展方向进行了展望,为探索全固态锂电池的实际生产应用提供理论指导。

关键词: 固态电解质, Li₇La₃Zr₂O₁₂, 全固态锂电池, 晶体结构, 离子电导率, 界面阻抗

Abstract: Solid-state electrolyte is the core component of all-solid-state lithium battery with the characteristics of high safety and high energy density. The typical representative Li₇La₃Zr₂O₁₂ (LLZO) has been paid extensive attention by researchers due to its high ionic conductivity, high mechanical strength, high electrochemical stability, low interfacial impedance, and good stability for lithium metal anodes. However, compared to liquid-state electrolytes, problems such as lower ionic conductivity and less contact with the solid-solid interface of electrodes in LLZO still exist. This research mainly introduced effects of the crystal structure and modification method of LLZO on its performances of ionic conductivity and interface impedance. Existing problems of LLZO were summarized, and future development directions were prospected. This research provides theoretical guidance for the practical production and application of all-solid-state lithium batteries.

Key words: solid-state electrolyte, Li₇La₃Zr₂O₁₂, all-solid-state lithium battery, crystal structure, ionic conductivity, interface impedance

中图分类号:

TQ131.11

李金瑶, 董生德, 马路祥, 周园. 石榴石型固态电解质Li₇La₃Zr₂O₁₂的改性研究现状[J]. 硅酸盐通报, 2022, 41(8): 2871-2878.

LI Jinyao, DONG Shengde, MA Luxiang, ZHOU Yuan. Recent Progress on Modification of Garnet Li₇La₃Zr₂O₁₂ Solid-State Electrolyte[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(8): 2871-2878.

参考文献

[1] TONG R A, CHEN L H, FAN B B, et al. Solvent-free process for blended PVDF-HFP/PEO and LLZTO composite solid electrolytes with enhanced mechanical and electrochemical properties for lithium metal batteries[J]. ACS Applied Energy Materials, 2021, 4(10): 11802-11812.
[2] MANTHIRAM A, YU X W, WANG S F. Lithium battery chemistries enabled by solid-state electrolytes[J]. Nature Reviews Materials, 2017, 2: 16103.
[3] AGRAWAL R C, GUPTA R K. Superionic solid: composite electrolyte phase: an overview[J]. Journal of Materials Science, 1999, 34(6): 1131-1162.
[4] 林碧霞,林小燕,邢震宇.稀土元素掺杂锂离子固态电解质的研究进展[J].中国稀土学报,2021,39(5):682-697.
LIN B X, LIN X Y, XING Z Y. Research advances of lithium-ion solid electrolytes doped with rare-earth elements[J]. Journal of the Chinese Society of Rare Earths, 2021, 39(5): 682-697 (in Chinese).
[5] MURUGAN R, THANGADURAI V, WEPPNER W. Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂[J]. Angewandte Chemie International Edition, 2007, 46(41): 7778-7781.
[6] KRAUSKOPF T, DIPPEL R, HARTMANN H, et al. Lithium-metal growth kinetics on LLZO garnet-type solid electrolytes[J]. Joule, 2019, 3(8): 2030-2049.
[7] SHEN Y B, ZHANG Y T, HAN S J, et al. Unlocking the energy capabilities of lithium metal electrode with solid-state electrolytes[J]. Joule, 2018, 2(9): 1674-1689.
[8] 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.
[9] PERVEZ S A, CAMBAZ M A, THANGADURAI V, et al. Interface in solid-state lithium battery: challenges, progress, and outlook[J]. ACS Applied Materials & Interfaces, 2019, 11(25): 22029-22050.
[10] ZHAO N, KHOKHAR W, BI Z J, et al. Solid garnet batteries[J]. Joule, 2019, 3(5): 1190-1199.
[11] 张阳.固态锂金属电池中石榴石型固态电解质/负极界面的改性研究[D].北京:中国科学院大学,2020.
ZHANG Y. Interfacial modification of anode/garnet-type solid-state electrolyte in solid-state lithium metal batteries[D]. Beijing: University of Chinese Academy of Sciences, 2020 (in Chinese).
[12] CUSSEN E J. Structure and ionic conductivity in lithium garnets[J]. Journal of Materials Chemistry, 2010, 20(25): 5167.
[13] O'CALLAGHAN M P, CUSSEN E J. Lithium dimer formation in the Li-conducting garnets Li_5+xBa_xLa_3-xTa₂O₁₂ (0＜x≤1.6)[J]. Chemical Communications (Cambridge, England), 2007(20): 2048-2050.
[14] THANGADURAI V, NARAYANAN S, PINZARU D. Garnet-type solid-state fast Li ion conductors for Li batteries: critical review[J]. Chemical Society Reviews, 2014, 43(13): 4714-4727.
[15] O'CALLAGHAN M P, LYNHAM D R, CUSSEN E J, et al. Structure and ionic-transport properties of lithium-containing garnets Li₃Ln₃Te₂O₁₂ (Ln: Y, Pr, Nd, Sm-Lu)[J]. ChemInform, 2006, 37(50): 4681-4689.
[16] 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.
[17] 姜鹏峰,石元盛,李康万,等.固态电解质锂镧锆氧(LLZO)的研究进展[J].储能科学与技术,2020,9(2):523-537.
JIANG P F, SHI Y S, LI K W, et al. Recent progress on the Li₇La₃Zr₂O₁₂ (LLZO) solid electrolyte[J]. Energy Storage Science and Technology, 2020, 9(2): 523-537 (in Chinese).
[18] AWAKA J, KIJIMA N, HAYAKAWA H, et al. Synthesis and structure analysis of tetragonal Li₇La₃Zr₂O₁₂ with the garnet-related type structure[J]. Journal of Solid State Chemistry, 2009, 182(8): 2046-2052.
[19] PERCIVAL J, KENDRICK E, SMITH R I, et al. Cation ordering in Li containing garnets: synthesis and structural characterisation of the tetragonal system, Li₇La₃Sn₂O₁₂[J]. Dalton Transactions, 2009(26): 5177.
[20] WANG C W, FU K, KAMMAMPATA S P, et al. Garnet-type solid-state electrolytes: materials, interfaces, and batteries[J]. Chemical Reviews, 2020, 120(10): 4257-4300.
[21] THOMPSON T, SHARAFI A, JOHANNES M D, et al. A tale of two sites: on defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries[J]. Advanced Energy Materials, 2015, 5(11): 1500096.
[22] PFENNINGER R, STRUZIK M, GARBAYO I, et al. A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films[J]. Nature Energy, 2019, 4(6): 475-483.
[23] XIE H, ALONSO J A, LI Y T, et al. Lithium distribution in aluminum-free cubic Li₇La₃Zr₂O₁₂[J]. Chemistry of Materials, 2011, 23(16): 3587-3589.
[24] 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.
[25] YANG X F, KONG D B, CHEN Z P, et al. Low-temperature fabrication for transparency Mg doping Li₇La₃Zr₂O₁₂ solid state electrolyte[J]. Journal of Materials Science: Materials in Electronics, 2018, 29(2): 1523-1529.
[26] ZHOU X R, HUANG L W, ELKEDIM O, et al. Sr²⁺ and Mo⁶⁺ co-doped Li₇La₃Zr₂O₁₂ with superior ionic conductivity[J]. Journal of Alloys and Compounds, 2022, 891: 161906.
[27] CAI L, WEN Z Y, RUI K. High ion conductivity in garnet-type F-doped Li₇La₃Zr₂O₁₂[J]. Journal of Inorganic Materials, 2015, 30(9): 995-1000.
[28] HUANG X, LU Y, SONG Z, et al. Manipulating Li₂O atmosphere for sintering dense Li₇La₃Zr₂O₁₂ solid electrolyte[J]. Energy Storage Materials, 2019, 22: 207-217.
[29] DERMENCI K B. Improved Li-ion conduction by ion-conductor Li_1.5Al_0.5Ge_1.5(PO₄)₃ additive in garnet type Li₇La₃Zr₂O₁₂ solid electrolytes[J]. Materials Chemistry and Physics, 2022, 281: 125910.
[30] CASTILLO A, CHARPENTIER T, RAPAUD O, et al. Bulk Li mobility enhancement in spark plasma sintered Li_(7-3x)Al_xLa₃Zr₂O₁₂ garnet[J]. Ceramics International, 2018, 44(15): 18844-18850.
[31] LAPTEV A M, ZHENG H, BRAM M, et al. High-pressure field assisted sintering of half-cell for all-solid-state battery[J]. Materials Letters, 2019, 247: 155-158.
[32] ZHA W P, XU Y H, CHEN F, et al. Cathode/electrolyte interface engineering via wet coating and hot pressing for all-solid-state lithium battery[J]. Solid State Ionics, 2019, 330: 54-59.
[33] IHRIG M, MISHRA T P, SCHELD W S, et al. Li₇La₃Zr₂O₁₂ solid electrolyte sintered by the ultrafast high-temperature method[J]. Journal of the European Ceramic Society, 2021, 41(12): 6075-6079.
[34] SHEN F, GUO W C, ZENG D Y, et al. A simple and highly efficient method toward high-density garnet-type LLZTO solid-state electrolyte[J]. ACS Applied Materials & Interfaces, 2020, 12(27): 30313-30319.
[35] YANG L, DAI Q S, LIU L, et al. Rapid sintering method for highly conductive Li₇La₃Zr₂O₁₂ ceramic electrolyte[J]. Ceramics International, 2020, 46(8): 10917-10924.
[36] YANG L, TAO X Y, HUANG X, et al. Efficient mutual-compensating Li-loss strategy toward highly conductive garnet ceramics for Li-metal solid-state batteries[J]. ACS Applied Materials & Interfaces, 2021, 13(47): 56054-56063.
[37] ZHENG J, HU Y Y. New insights into the compositional dependence of Li-ion transport in polymer-ceramic composite electrolytes[J]. ACS Applied Materials & Interfaces, 2018, 10(4): 4113-4120.
[38] 金英敏,李栋,贾政刚,等.用于全固态锂电池的有机-无机复合电解质[J].原子与分子物理学报,2020,37(6):958-973.
JIN Y M, LI D, JIA Z G, et al. Organic-inorganic composite electrolytes for all-solid-state lithium batteries[J]. Journal of Atomic and Molecular Physics, 2020, 37(6): 958-973 (in Chinese).
[39] HUO H Y, CHEN Y, LUO J, et al. Rational design of hierarchical “ceramic-in-polymer” and “polymer-in-ceramic” electrolytes for dendrite-free solid-state batteries[J]. Advanced Energy Materials, 2019, 9(17): 1804004.
[40] CHEN L, LI Y T, LI S P, et al. PEO/garnet composite electrolytes for solid-state lithium batteries: from “ceramic-in-polymer” to “polymer-in-ceramic”[J]. Nano Energy, 2018, 46: 176-184.
[41] XIE H, YANG C P, FU K, et al. Flexible, scalable, and highly conductive garnet-polymer solid electrolyte templated by bacterial cellulose[J]. Advanced Energy Materials, 2018, 8(18): 1703474.
[42] FU K, GONG Y H, FU Z Z, et al. Transient behavior of the metal interface in lithium metal-garnet batteries[J]. Angewandte Chemie International Edition, 2017, 56(47): 14942-14947.
[43] HAN X G, GONG Y H, FU K, et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries[J]. Nature Materials, 2017, 16(5): 572-579.
[44] FU J M, YU P F, ZHANG N, et al. In situ formation of a bifunctional interlayer enabled by a conversion reaction to initiatively prevent lithium dendrites in a garnet solid electrolyte[J]. Energy & Environmental Science, 2019, 12(4): 1404-1412.

石榴石型固态电解质Li₇La₃Zr₂O₁₂的改性研究现状

Recent Progress on Modification of Garnet Li₇La₃Zr₂O₁₂ Solid-State Electrolyte

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