Top

Published in:

18-11-2023 | Original Article

A lithium–tin fluoride anode enabled by ionic/electronic conductive paths for garnet-based solid-state lithium metal batteries

Authors: Lei Zhang, Qian-Kun Meng, Xiang-Ping Feng, Ming Shen, Yu-Qing Zhang, Quan-Chao Zhuang, Run-Guo Zheng, Zhi-Yuan Wang, Yan-Hua Cui, Hong-Yu Sun, Yan-Guo Liu

Published in: Rare Metals | Issue 2/2024

Activate our intelligent search to find suitable subject content or patents.

search-config

AI-assisted search

Off

Abstract

The high energy density and stability of solid-state lithium metal batteries (SSLMBs) have garnered great attention. Garnet-type oxides, especially Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO), with high ionic conductivity, wide electrochemical window, and stability to Li metal anode, are promising solid-state electrolyte (SSEs) materials for SSLMBs. However, Li/LLZTO interface issues including high interface resistance, inhomogeneous Li deposition, and Li dendrite growth have hindered the practical application of SSLMBs. Herein, a multi-functional Li–SnF₂ composite anode with Li, LiF, and Li-Sn alloy was specifically designed and prepared. The composite anode improves the wettability to LLZTO, constructing an intimate contact interface between it and LLZTO. Meanwhile, ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li dendrite. The solid-state symmetric cell exhibits low interface resistance (11 Ω·cm²) and high critical current density (1.3 mA·cm⁻²) at 25 °C. The full SSLMB based on LiFePO₄ or LiNi_0.5Co_0.2Mn_0.3O₂ cathode also shows stable cycling performance and high rate capability. This work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.

Graphical abstract

previous article Lithium-induced graphene layer containing Li3P alloy phase to achieve ultra-stable electrode interface for lithium metal anode

next article Engineering molecular regulation for SiOx with long-term stable cycle and high Coulombic efficiency as lithium-ion battery anodes

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

über 102.000 Bücher
über 537 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Finance + Banking
Management + Führung
Marketing + Vertrieb
Maschinenbau + Werkstoffe
Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

über 67.000 Bücher
über 390 Zeitschriften

aus folgenden Fachgebieten:

Automobil + Motoren
Bauwesen + Immobilien
Business IT + Informatik
Elektrotechnik + Elektronik
Energie + Nachhaltigkeit
Maschinenbau + Werkstoffe

Jetzt Wissensvorsprung sichern!

inform now

Available only for authorised users

[1]

Ye LH, Li X. A dynamic stability design strategy for lithium metal solid state batteries. Nature. 2021;593(7858):218. https://doi.org/10.1038/s41586-021-03486-3.CrossRef

[2]

Wang D, Tian KH, Wang J, Wang ZY, Luo SH, Liu YG, Wang Q, Zhang YH, Hao AM, Yi TF. Sulfur-doped 3D hierarchical porous carbon network toward excellent potassium-ion storage performance. Rare Met. 2021;40(9):2464. https://doi.org/10.1007/s12598-021-01715-2.CrossRef

[3]

Zhao Q, Stalin S, Zhao CZ, Archer LA. Designing solid-state electrolytes for safe, energy-dense batteries. Nat Rev Mater. 2020;5(3):229. https://doi.org/10.1038/s41578-019-0165-5.CrossRef

[4]

Guo YM, Zhang LJ, Xi LD, Kang J. Advances of carbon materials as loaders for transition metal oxygen/sulfide anode materials. Rare Met. 2021;45(10):1241. https://doi.org/10.13373/j.cnki.cjrm.XY20040016.CrossRef

[5]

Song SP, Yang C, Jiang CZ, Wu YM, Guo R, Sun H, Yang JL, Xiang Y, Zhang XK. Increasing ionic conductivity in Li_0.33La_0.56TiO₃ thin-films via optimization of processing atmosphere and temperature. Rare Met. 2022;41(1):179. https://doi.org/10.1007/s12598-021-01782-5.CrossRef

[6]

Zhang L, Fan HL, Dang YZ, Zhuang QC, Arandiyan H, Wang Y, Cheng NY, Sun HY, Garza HHP, Zheng RG, Wang ZY, Mofarah SS, Koshy P, Bhargava SK, Cui YH, Shao ZP, Liu YG. Recent advances in in situ and operando characterization techniques for Li₇La₃Zr₂O₁₂-based solid-state lithium batteries. Mater Horizons. 2023;10(5):1479. https://doi.org/10.1039/d3mh00135k.CrossRef

[7]

Zhang L, Zhuang QC, Zheng RG, Wang ZY, Sun HY, Arandiyan H, Wang Y, Liu YG, Shao ZP. Recent advances of Li₇La₃Zr₂O₁₂-based solid-state lithium batteries towards high energy density. Energy Storage Mater. 2022;49:299. https://doi.org/10.1016/j.ensm.2022.04.026.CrossRef

[8]

Chen LH, Huang ZY, Chen SL, Tong RA, Wang HL, Shao G, Wang CA. In situ polymerization of 1,3-dioxolane infiltrating 3D garnet framework with high ionic conductivity and excellent interfacial stability for integrated solid-state Li metal battery. Rare Met. 2022;41(11):3694. https://doi.org/10.1007/s12598-022-02080-4.CrossRef

[9]

Yoon K, Lee S, Oh K, Kang K. Challenges and strategies towards practically feasible solid-state lithium metal batteries. Adv Mater. 2022;34(4):2104666. https://doi.org/10.1002/adma.202104666.CrossRef

[10]

Han X, Chen JZ, Chen MF, Zhou WJ, Zhou XY, Wang GW, Wong CP, Liu B, Luo LS, Chen SY, Shi SQ. Induction of planar Li growth with designed interphases for dendrite-free Li metal anodes. Energy Storage Mater. 2021;39:250. https://doi.org/10.1016/j.ensm.2021.04.029.CrossRef

[11]

Han X, Wang SY, Xu YB, Zhong GM, Zhou Y, Liu B, Jiang XY, Wang X, Li Y, Zhang ZQ, Chen SY, Wang CM, Yang Y, Zhang WQ, Wang JL, Liu J, Yang JH. All solid thick oxide cathodes based on low temperature sintering for high energy solid batteries. Energy Environ Sci. 2021;14(9):5044. https://doi.org/10.1039/d1ee01494c.CrossRef

[12]

Zhao C, Liu ZQ, Weng W, Wu M, Yan XY, Yang J, Lu HM, Yao XY. Stabilized cathode/sulfide solid electrolyte interface via Li2ZrO3 coating for all-solid-state batteries. Rare Met. 2022;41(11):3639. https://doi.org/10.1007/s12598-022-02086-y.CrossRef

[13]

Xiao YH, Wang Y, Bo SH, Kim JC, Miara LJ, Ceder G. Understanding interface stability in solid-state batteries. Nat Rev Mater. 2020;5(2):105. https://doi.org/10.1038/s41578-019-0157-5.CrossRef

[14]

Lv Q, Jiang YP, Wang B, Chen YJ, Jin F, Wu BC, Ren HZ, Zhang N, Xu RY, Li YH, Zhang TR, Zhou Y, Wang DL, Liu HK, Dou SX. Suppressing lithium dendrites within inorganic solid-state electrolytes. Cell Rep Phys Sci. 2022;3(1):100706. https://doi.org/10.1016/j.xcrp.2021.100706.CrossRef

[15]

Yang LJ, Lu ZL, Qin YX, Wu C, Fu CK, Gao YZ, Liu J, Jiang L, Du ZY, Xie ZY, Li ZQ, Kong FD, Yin GP. Interrelated interfacial issues between a Li₇La₃Zr₂O₁₂-based garnet electrolyte and Li anode in the solid-state lithium battery: a review. J Mater Chem A. 2021;9(10):5952. https://doi.org/10.1039/d0ta08179e.CrossRef

[16]

Sharafi A, Yu SH, Naguib M, Lee M, Ma C, Meyer HM, Nanda J, Chi MF, Siegel DJ, Sakamoto J. Impact of air exposure and surface chemistry on Li-Li₇La₃Zr₂O₁₂ interfacial resistance. J Mater Chem A. 2017;5(26):13475. https://doi.org/10.1039/c7ta03162a.CrossRef

[17]

Jin Y, McGinn PJ. Li₇La₃Zr₂O₁₂ electrolyte stability in air and fabrication of a Li/Li₇La₃Zr₂O₁₂/Cu_0.1V₂O₅ solid-state battery. J Power Sources. 2013;239:326. https://doi.org/10.1016/j.jpowsour.2013.03.155.CrossRef

[18]

Guo Y, Cheng J, Zeng Z, Li Y, Zhang H, Li D, Ci L. Li₂CO₃: insights into its blocking effect on Li-ion transfer in garnet composite electrolytes. ACS Appl Energy Mater. 2022;5(3):2853–61. https://doi.org/10.1021/acsaem.1c03529.CrossRef

[19]

Qin ZW, Xie YM, Meng XC, Qian DL, Shan C, Mao DX, He G, Zheng Z, Wan L, Huang YX. Interface engineering for garnet-type electrolyte enables low interfacial resistance in solid-state lithium batteries. Chem Eng J. 2022;447:137538. https://doi.org/10.1016/j.cej.2022.137538.CrossRef

[20]

Ruan Y, Lu Y, Huang X, Su J, Sun C, Jin J, Wen ZY. Acid induced conversion towards a robust and lithiophilic interface for Li-Li₇La₃Zr₂O₁₂ solid-state batteries. J Mater Chem A. 2019;7(24):14565. https://doi.org/10.1039/c9ta01911a.CrossRef

[21]

Huo HY, Chen Y, Zhao N, Lin XT, Luo J, Yang XF, Liu YL, Guo XX, Sun XL. In-situ formed Li₂CO₃-free garnet/Li interface by rapid acid treatment for dendrite-free solid-state batteries. Nano Energy. 2019;61:119. https://doi.org/10.1016/j.nanoen.2019.04.058.CrossRef

[22]

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. https://doi.org/10.1021/jacs.8b03106.CrossRef

[23]

Wang X, Shen X, Zhang P, Zhou AJ, Zhao JB. Promoted Li⁺ conduction in PEO-based all-solid-state electrolyte by hydroxyl-modified glass fiber fillers. Rare Met. 2022;42(3):875. https://doi.org/10.1007/s12598-022-02218-4.CrossRef

[24]

Sharafi A, Kazyak E, Davis AL, Yu SH, Thompson T, Siegel DJ, Dasgupta NP, Sakamoto J. Surface chemistry mechanism of ultra-low interfacial resistance in the solid-state electrolyte Li₇La₃Zr₂O₁₂. Chem Mat. 2017;29(18):7961. https://doi.org/10.1021/acs.chemmater.7b03002.CrossRef

[25]

Xu HF, Zhu Q, Zhao Y, Du ZG, Li B, Yang SB. Phase-changeable dynamic conformal electrode/electrolyte interlayer enabling pressure-independent solid-state lithium metal batteries. Adv Mater. 2023;35(18):2212111. https://doi.org/10.1002/adma.202212111.CrossRef

[26]

Liu M, Xie WH, Li B, Wang YB, Li GQ, Zhang ST, Wen YH, Qiu JY, Chen JH, Zhao PC. Garnet Li₇La₃Zr₂O₁₂-based solid-state lithium batteries achieved by in situ thermally polymerized gel polymer electrolyte. ACS Appl Mater Interfaces. 2022;14(38):43116. https://doi.org/10.1021/acsami.2c09028.CrossRef

[27]

Gutierrez-Pardo A, Aguesse F, Fernandez-Carretero F, Siriwardana AI, Garcia-Luis A, Llordes A. Improved electromechanical stability of the Li metal/garnet ceramic interface by a solvent-free deposited OIPC soft layer. ACS Appl Energy Mater. 2021;4(3):2388. https://doi.org/10.1021/acsaem.0c02439.CrossRef

[28]

Dubey R, Sastre J, Cancellieri C, Okur F, Forster A, Pompizii L, Priebe A, Romanyuk YE, Jeurgens LPH, Kovalenko MV, Kravchyk KV. Building a better Li-garnet solid electrolyte/metallic Li interface with antimony. Adv Energy Mater. 2021;11(39):2102086. https://doi.org/10.1002/aenm.202102086.CrossRef

[29]

Cui J, Kim JH, Yao SS, Guerfi A, Paolella A, Goodenough JB, Khani H. Exploration of metal alloys as zero-resistance interfacial modification layers for garnet-type solid electrolytes. Adv Funct Mater. 2023;33(10):2210192. https://doi.org/10.1002/adfm.202210192.CrossRef

[30]

Liao JL, Zhang S, Bai TS, Ji FJ, Li DP, Cheng J, Zhang HQ, Lu JY, Gao Q, Ci LJ. A ZnO decorated 3D copper foam as a lithiophilic host to construct composite lithium metal anodes for Li-O₂ batteries. Rare Met. 2023;42(6):1969. https://doi.org/10.1007/s12598-023-02281-5.CrossRef

[31]

Liang YH, Wu WB, Li DP, Wu H, Gao CC, Chen ZJ, Ci LJ, Zhang JH. Highly stable lithium metal batteries by regulating the lithium nitrate chemistry with a modified eutectic electrolyte. Adv Energy Mater. 2022;12(47):2202493. https://doi.org/10.1002/aenm.202202493.CrossRef

[32]

Zhu FJ, Deng WT, Zhang BC, Wang HJ, Xu LQ, Liu HX, Luo Z, Zou GQ, Hou HS, Ji XB. In-situ construction of multifunctional interlayer enabled dendrite-free garnet-based solid-state batteries. Nano Energy. 2023;111:108416. https://doi.org/10.1016/j.nanoen.2023.108416.CrossRef

[33]

Chen Y, Qian J, Hu X, Ma YT, Li Y, Xue TY, Yu TY, Li L, Wu F, Chen RJ. Constructing a uniform and stable mixed conductive layer to stabilize the solid-state electrolyte/Li interface by cold bonding at mild conditions. Adv Mater. 2023;35(18):2212096. https://doi.org/10.1002/adma.202212096.CrossRef

[34]

Chen BT, Zhang JC, Zhang TR, Wang RY, Zheng J, Zhai YW, Liu XF. Constructing a superlithiophilic 3D burr-microsphere interface on garnet for high-rate and ultra-stable solid-state Li batteries. Adv Sci. 2023;10(11):2207056. https://doi.org/10.1002/advs.202207056.CrossRef

[35]

Dai QS, Yao JM, Du CC, Ye HJ, Gao ZY, Zhao J, Chen JZ, Su Y, Li H, Fu XJ, Yan JT, Zhu DD, Zhang XD, Li MY, Luo ZY, Qiu HL, Huang Q, Zhang LQ, Tang YF, Huang JY. Cryo-EM studies of atomic-scale structures of interfaces in garnet-type electrolyte based solid-state batteries. Adv Funct Mater. 2022;32(51):2208682. https://doi.org/10.1002/adfm.202208682.CrossRef

[36]

Duan J, Wu WY, Nolan AM, Wang TR, Wen JY, Hu CC, Mo YF, Luo W, Huang YH. Lithium-graphite paste: an interface compatible anode for solid-state batteries. Adv Mater. 2019;31(10):1807243. https://doi.org/10.1002/adma.201807243.CrossRef

[37]

Liu YN, Xiao Z, Zhang WK, Zhang J, Huang H, Gan YP, He XP, Kumar GG, Xia Y. Poly(m-phenylene isophthalamide)-reinforced polyethylene oxide composite electrolyte with high mechanical strength and thermostability for all-solid-state lithium metal batteries. Rare Met. 2022;41(11):3762. https://doi.org/10.1007/s12598-022-02065-3.CrossRef

[38]

Han FD, Westover AS, Yue J, Fan XL, Wang F, Chi MF, Leonard DN, Dudney N, Wang H, Wang CS. High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes. Nat Energy. 2019;4(3):187. https://doi.org/10.1038/s41560-018-0312-z.CrossRef

[39]

Liu XM, Garcia-Mendez R, Lupini AR, Cheng YQ, Hood ZD, Han FD, Sharafi A, Idrobo JC, Dudney NJ, Wang CS, Ma C, Sakamoto J, Chi MF. Local electronic structure variation resulting in Li “filament” formation within solid electrolytes. Nat Mater. 2021;20(11):1485. https://doi.org/10.1038/s41563-021-01019-x.CrossRef

[40]

Wei J, Yang ZG, Lu GJ, Hu XL, Li ZY, Wang RH, Xu CH. Enabling an electron/ion conductive composite lithium anode for solid-state lithium-metal batteries with garnet electrolyte. Energy Storage Mater. 2022;53:204. https://doi.org/10.1016/j.ensm.2022.08.041.CrossRef

[41]

Huang YL, Shao BW, Han FD. Li alloy anodes for high-rate and high-areal-capacity solid-state batteries. J Mater Chem A. 2022;10(23):12350. https://doi.org/10.1039/d2ta02339c.CrossRef

[42]

Jain A, Ong SP, Hautier G, Chen W, Richards WD, Dacek S, Cholia S, Gunter D, Skinner D, Ceder G, Persson KA. Commentary: the materials project: a materials genome approach to accelerating materials innovation. APL Mater. 2013;1(1):011002. https://doi.org/10.1063/1.4812323.CrossRef

[43]

Lee K, Han S, Lee J, Lee S, Kim J, Ko YM, Kim S, Yoon K, Song JH, Noh JH, Kang K. Multifunctional interface for high-rate and long-durable garnet-type solid electrolyte in lithium metal batteries. ACS Energy Lett. 2022;7(1):381. https://doi.org/10.1021/acsenergylett.1c02332.CrossRef

[44]

Zhao B, Ma WC, Li BB, Hu XT, Lu SY, Liu XY, Jiang Y, Zhang JJ. A fast and low-cost interface modification method to achieve high-performance garnet-based solid-state lithium metal batteries. Nano Energy. 2022;91:10. https://doi.org/10.1016/j.nanoen.2021.106643.CrossRef

[45]

Chen L, Tong RA, Zhang J, Wang H, Shao G, Dong Y, Wang CA. Reactive magnesium nitride additive: a drop-in solution for lithium/garnet wetting in all-solid-state batteries. Angew Chem-Int Edit. 2023;62(27):e202305099. https://doi.org/10.1002/anie.202305099.CrossRef

[46]

Santhosha AL, Medenbach L, Buchheim JR, Adelhelm P. The indium-lithium electrode in solid-state lithium-ion batteries: phase formation, redox potentials, and interface stability. Batteries Supercaps. 2019;2(6):524. https://doi.org/10.1002/batt.201800149.CrossRef

[47]

Raj V, Venturi V, Kankanallu VR, Kuiri B, Viswanathan V, Aetukuri NPB. Direct correlation between void formation and lithium dendrite growth in solid-state electrolytes with interlayers. Nat Mater. 2022;21(9):1050. https://doi.org/10.1038/s41563-022-01264-8.CrossRef

[48]

Cui J, Yao SS, Guerfi A, Kim C, Goodenough JB, Khani H. Melt-quenching of artificial metallic interlayer enables a resistance-free garnet/lithium interface for all-solid-state lithium-metal batteries. Energy Storage Mater. 2022;53:899. https://doi.org/10.1016/j.ensm.2022.10.002.CrossRef

[49]

Wan Z, Shi K, Huang Y, Yang L, Yun Q, Chen L, He YB. Three-dimensional alloy interface between Li_6.4La₃Zr_1.4Ta_0.6O₁₂ and Li metal to achieve excellent cycling stability of all-solid-state battery. J Power Sour. 2021;505:230062. https://doi.org/10.1016/j.jpowsour.2021.230062.CrossRef

[50]

Zhang L, Meng QK, Dai Y, Feng XP, Shen M, Zhuang QC, Ju ZC, Zheng RG, Wang ZY, Cui YH, Sun HY, Liu YG. Ion/electron conductive layer with double-layer-like structure for dendrite-free solid-state lithium metal batteries. Nano Energy. 2023;113:108573. https://doi.org/10.1016/j.nanoen.2023.108573.CrossRef

[51]

Cheng AR, He X, Wang RX, Shan B, Wang KL, Jiang K. Low-cost molten salt coating enabling robust Li/garnet interface for dendrite-free all-solid-state lithium batteries. Chem Eng J. 2022;450:138236. https://doi.org/10.1016/j.cej.2022.138236.CrossRef

[52]

Wang TR, Duan J, Zhang B, Luo W, Ji X, Xu HH, Huang Y, Huang LQ, Song ZY, Wen JY, Wang CS, Huang YH, Goodenough JB. A self-regulated gradient interphase for dendrite-free solid-state Li batteries. Energy Environ Sci. 2022;15(3):1325. https://doi.org/10.1039/d1ee03604a.CrossRef

[53]

Zhao B, Ma W, Li B, Hu X, Lu S, Liu X, Jiang Y, Zhang J. A fast and low-cost interface modification method to achieve high-performance garnet-based solid-state lithium metal batteries. Nano Energy. 2022;91:106643. https://doi.org/10.1016/j.nanoen.2021.106643.CrossRef

Title: A lithium–tin fluoride anode enabled by ionic/electronic conductive paths for garnet-based solid-state lithium metal batteries
Authors: Lei Zhang
Qian-Kun Meng
Xiang-Ping Feng
Ming Shen
Yu-Qing Zhang
Quan-Chao Zhuang
Run-Guo Zheng
Zhi-Yuan Wang
Yan-Hua Cui
Hong-Yu Sun
Yan-Guo Liu
Publication date: 18-11-2023
Publisher: Nonferrous Metals Society of China
Published in: Rare Metals / Issue 2/2024
Print ISSN: 1001-0521
Electronic ISSN: 1867-7185
DOI: https://doi.org/10.1007/s12598-023-02468-w

Springer Professional

Abstract

Graphical abstract

Please log in to get access to your license.

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Springer Professional "Technik"

Other articles of this Issue 2/2024

Integration of urchin-like MnCo2O4@C core–shell nanowire arrays within porous copper current collector for superior performance Li-ion battery anodes

Recent advances in vacancy engineering for reliable lithium-sulfur batteries

Fast charge transfer kinetics in Sv-ZnIn2S4/Sb2S3 S-scheme heterojunction photocatalyst for enhanced photocatalytic hydrogen evolution

Regulating interfacial stability of SiOx anode with fluoride-abundant solid–electrolyte interphase by fluorine-functionalized additive

Work-function-induced interfacial electron redistribution of MoO2/WO2 heterostructures for high-efficiency electrocatalytic hydrogen evolution reaction

Insight into vertical piezoelectric characteristics regulated thermal transport in van der Waals two-dimensional materials

Premium Partners