Recent Progress on Modification of Garnet Li7La3Zr2O12 Solid-State Electrolyte

Abstract

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

CLC Number:

TQ131.11

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.

References

[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.

Recent Progress on Modification of Garnet Li₇La₃Zr₂O₁₂ Solid-State Electrolyte

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 12

Recommended Articles

Metrics

Comments

[1]	LIU Xinnan, XIAO Yanzhi, HUANG Meiqi, JIANG Han, KONG Jiangrong, ZHOU Tao. Properties of LSCM-GDC Composite Cathode Impregnatedwith Ni and Cu [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2022, 41(7): 2458-2466.
[2]	CHEN Qingjie, ZHOU Junhu, GUAN Xiping, YANG Bingbing, YANG Jinjiao, LI Nan. Influence of Chemical Composition on Structure and Properties of Light-Burned Magnesium-Aluminum Spinel [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(4): 1388-1394.
[3]	HUANG Jian;ZHU Yang;HUANG Hao;MA Bao-guo. Atmospheric Pressure Hydrothermal Synthesis and Thermal Stability Analysis of Alkaline Metal Doped Calcium Sulfate Short Whiskers [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2017, 36(11): 3581-3586.
[4]	ZHANG Zu-kang;WANG Ying. Synthesis,Crystal Structures and Properties of Two Pb(Ⅱ)/Cd(Ⅱ) Complexes of Crystalline Fluorescent Materials [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2016, 35(8): 2518-2523.
[5]	WANG Liang;YAN Ke-jun. Mechanism of Polymeric Ferric Sulfate(PFS) Solutions Effected by Alternative Magnetic Fields [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2016, 35(7): 2298-2303.
[6]	DAI Pei-xia;GE Hong-guang. Synthesis, Crystal Structure and Fluorescent Property of Complex [Cd(na) 2 (phen) 2] · [Cd(na) 2 (phen) 2] · 3H2O [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2016, 35(4): 1028-1033.
[7]	WANG Fei;CHEN Hui-hui. Effect of Pre-press Forming on Spectral Properties of Phosphors CaAl2Si2O8∶ Eu3+, Li+ [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2016, 35(12): 3998-4004.
[8]	WANG Ying;ZHANG Bo;REN Hao;GUAN Lei. Synthesis, Structure and Properties of a Novel Mononuclear Zinc Complex of Crystalline Material Containing Nitrogen-Donor Ligand [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2016, 35(11): 3704-3708.
[9]	WANG Yue;WANG Lan;WANG Xin;LIU Yao-jun;WEI Li-ying. Incorporation Behavior of Cr3+ Ion in the Tricalcium Silicate [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2013, 32(7): 1253-1257.
[10]	PAN Chun-yang;MAI Hai-deng;LU Jing;LI Da-guang;YANG Hong-mei;ZHAO Feng-hua;ZHENG Ying-lin. Synthesis and Luminescent Property of Organic Templated Pentaborate [C2H8N] [B5O6(OH)4] [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2013, 32(12): 2417-2420.
[11]	OUYANG Ping;LI Da-guang;PAN Chun-yang;CAI Wei-xian. Structure of (NH_4)_2[B_(10)O_(14)(OH)_4]·H_2O Based on Scale Chemistry and Discussion of Synthesis Mechanism [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2010, 29(1): 53-57.
[12]	CHEN Fei;ZHOU Hong-qing;ZHU Hai-kui;WEI Peng-fei;CHEN Dong;LIU Min. Research Progress in Preparation and Electric Properties of (Zr, Sn)TiO_4 Thin Films [J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2009, 28(5): 986-990.