Recent progress in constructing fluorinated solid–electrolyte interphases for stable lithium metal anodes

Di Zhang; Pengfei Lv; Wei Qin; Xin He; Yuanhua He

doi:10.1007/s12613-024-2996-3

Article Contents

Article Navigation > International Journal of Minerals, Metallurgy and Materials > 2025 > In press, Uncorrected proof

Di Zhang, Pengfei Lv, Wei Qin, Xin He, and Yuanhua He, Recent progress in constructing fluorinated solid–electrolyte interphases for stable lithium metal anodes, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2996-3

Cite this article as:

Di Zhang, Pengfei Lv, Wei Qin, Xin He, and Yuanhua He, Recent progress in constructing fluorinated solid–electrolyte interphases for stable lithium metal anodes, Int. J. Miner. Metall. Mater.,(2025). https://doi.org/10.1007/s12613-024-2996-3

Citation:

PDF( 5504 KB)

Review

Recent progress in constructing fluorinated solid–electrolyte interphases for stable lithium metal anodes

+ Author Affiliations

Corresponding authors:
Xin He E-mail: xinhe@scu.edu.cn

Yuanhua He E-mail: heyuanhua@cafuc.edu.cn
Received: 3 April 2024; Revised: 25 August 2024; Accepted: 27 August 2024; Available online: 30 August 2024

Abstract

Abstract

Lithium metal batteries (LMBs) are emerging as a promising energy storage solution owing to their high energy density and specific capacity. However, the non-uniform plating of lithium and the potential rupture of the solid–electrolyte interphase (SEI) during extended cycling use may result in dendrite growth, which can penetrate the separator and pose significant short-circuit risks. Forming a stable SEI is essential for the long-term operation of the batteries. Fluorine-rich SEI has garnered significant attention for its ability to effectively passivate electrodes, regulate lithium deposition, and inhibit electrolyte corrosion. Understanding the structural components and preparation methods of existing fluorinated SEI is crucial for optimizing lithium metal anode performance. This paper reviews the research on optimizing LiF passivation interfaces to protect lithium metal anodes. It focuses on four types of compositions in fluorinated SEI that work synergistically to enhance SEI performance. For instance, combining compounds with LiF can further enhance the mechanical strength and ionic conductivity of the SEI. Integrating metals with LiF significantly improves electrochemical performance at the SEI/anode interface, with a necessary focus on reducing electron tunneling risks. Additionally, incorporating polymers with LiF offers balanced improvements in interfacial toughness and ionic conductivity, though maintaining structural stability over long cycles remains a critical area for future research. Although alloys combined with LiF increase surface energy and lithium affinity, challenges such as dendrite growth and volume expansion persist. In summary, this paper emphasizes the crucial role of interfacial structures in LMBs and offers comprehensive guidance for future design and development efforts in battery technology.
- LiF;
- lithium metal anodes;
- solid–electrolyte interphase;
- interface;
- cycling stability

FullText(HTML)

Supplements(0)

References(95)

References

[1]	T. Placke, R. Kloepsch, S. Dühnen, and M. Winter, Lithium ion, lithium metal, and alternative rechargeable battery technologies: The odyssey for high energy density, J. Solid State Electrochem., 21(2017), No. 7, p. 1939. doi: 10.1007/s10008-017-3610-7
[2]	L. Grande, E. Paillard, J. Hassoun, et al., The lithium/air battery: Still an emerging system or a practical reality?, Adv. Mater., 27(2015), No. 5, p. 784. doi: 10.1002/adma.201403064
[3]	P. Albertus, S. Babinec, S. Litzelman, and A. Newman, Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries, Nat. Energy, 3(2018), p. 16.
[4]	J. Heine, P. Hilbig, X. Qi, P. Niehoff, M. Winter, and P. Bieker, Fluoroethylene carbonate as electrolyte additive in tetraethylene glycol dimethyl ether based electrolytes for application in lithium ion and lithium metal batteries, J. Electrochem. Soc., 162(2015), No. 6, p. A1094. doi: 10.1149/2.0011507jes
[5]	K.Z. Cao, S.T. Wang, Y.N. He, J.H. Ma, Z.W. Yue, and H.Q. Liu, Constructing Al@C–Sn pellet anode without passivation layer for lithium-ion battery, Int. J. Miner. Metall. Mater., 31(2024), No. 3, p. 552. doi: 10.1007/s12613-023-2720-8
[6]	T. Wei, Q. Zhang, S.J. Wang, et al., A gel polymer electrolyte with IL@UiO-66–NH₂ as fillers for high-performance all-solid-state lithium metal batteries, Int. J. Miner. Metall. Mater., 30(2023), No. 10, p. 1897. doi: 10.1007/s12613-023-2639-0
[7]	W.D. Zhang, Q. Wu, J.X. Huang, et al., Colossal granular lithium deposits enabled by the grain-coarsening effect for high-efficiency lithium metal full batteries, Adv. Mater., 32(2020), No. 24, art. No. 2001740. doi: 10.1002/adma.202001740
[8]	X.L. Chen, Y.D. Gong, X. Li, F. Zhan, X.H. Liu, and J.M. Ma, Perspective on low-temperature electrolytes for LiFePO₄-based lithium-ion batteries, Int. J. Miner. Metall. Mater., 30(2023), No. 1, p. 1. doi: 10.1007/s12613-022-2541-1
[9]	X.B. Cheng, J.Q. Huang, and Q. Zhang, Review—Li metal anode in working lithium–sulfur batteries, J. Electrochem. Soc., 165(2017), No. 1, p. A6058.
[10]	X.B. Cheng, C. Yan, X.Q. Zhang, H. Liu, and Q. Zhang, Electronic and ionic channels in working interfaces of lithium metal anodes, ACS Energy Lett., 3(2018), No. 7, p. 1564. doi: 10.1021/acsenergylett.8b00526
[11]	Y.Y. Lu, Z.Y. Tu, and L.A. Archer, Stable lithium electrodeposition in liquid and nanoporous solid electrolytes, Nat. Mater., 13(2014), No. 10, p. 961. doi: 10.1038/nmat4041
[12]	K. Yan, Z.D. Lu, H.W. Lee, et al., Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth, Nat. Energy, 1(2016), No. 3, art. No. 16010. doi: 10.1038/nenergy.2016.10
[13]	E. Peled, Film forming reaction at the lithium/electrolyte interface, J. Power Sources, 9(1983), No. 3, p. 253. doi: 10.1016/0378-7753(83)87026-8
[14]	Y.F. Zhou, M. Su, X.F. Yu, et al., Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery, Nat. Nanotechnol., 15(2020), No. 3, p. 224. doi: 10.1038/s41565-019-0618-4
[15]	G. Nazri and R.H. Muller, Composition of surface layers on Li electrodes in PC, LiClO₄ of very low water content, J. Electrochem. Soc., 132(1985), No. 9, p. 2050. doi: 10.1149/1.2114288
[16]	D. Aurbach, M.L. Daroux, P.W. Faguy, and E. Yeager, Identification of surface films formed on lithium in propylene carbonate solutions, J. Electrochem. Soc., 134(1987), No. 7, art. No. 1611. doi: 10.1149/1.2100722
[17]	M. Garreau, Cyclability of the lithium electrode, J. Power Sources, 20(1987), No. 1-2, p. 9. doi: 10.1016/0378-7753(87)80085-X
[18]	J. Thevenin, Passivating films on lithium electrodes. An approach by means of electrode impedance spectroscopy, J. Power Sources, 14(1985), No. 1-3, p. 45. doi: 10.1016/0378-7753(85)88009-5
[19]	J.G. Thevenin and R.H. Muller, Impedance of lithium electrodes in a propylene carbonate electrolyte, J. Electrochem. Soc., 134(1987), No. 2, p. 273. doi: 10.1149/1.2100445
[20]	S.S. Zhang, K. Xu, and T.R. Jow, Enhanced performance of Li-ion cell with LiBF₄–PC based electrolyte by addition of small amount of LiBOB, J. Power Sources, 156(2006), No. 2, p. 629. doi: 10.1016/j.jpowsour.2005.04.023
[21]	G.W. Zheng and T. Wei, Batteries: Just a spoonful of LiPF₆, Nat. Energy, 2(2017), No. 3, art. No. 17029. doi: 10.1038/nenergy.2017.29
[22]	T.Z. Hou, G. Yang, N.N. Rajput, et al., The influence of FEC on the solvation structure and reduction reaction of LiPF₆/EC electrolytes and its implication for solid electrolyte interphase formation, Nano Energy, 64(2019), art. No. 103881. doi: 10.1016/j.nanoen.2019.103881
[23]	J. Ko and Y.S. Yoon, Recent progress in LiF materials for safe lithium metal anode of rechargeable batteries: Is LiF the key to commercializing Li metal batteries?, Ceram. Int., 45(2019), No. 1, p. 30. doi: 10.1016/j.ceramint.2018.09.287
[24]	T. Li, X.Q. Zhang, P. Shi, and Q. Zhang, Fluorinated solid–electrolyte interphase in high-voltage lithium metal batteries, Joule, 3(2019), No. 11, p. 2647. doi: 10.1016/j.joule.2019.09.022
[25]	J. Zhao, L. Liao, F.F. Shi, et al., Surface fluorination of reactive battery anode materials for enhanced stability, J. Am. Chem. Soc., 139(2017), No. 33, p. 11550. doi: 10.1021/jacs.7b05251
[26]	Y.Y. Liu, D.C. Lin, Y.Z. Li, et al., Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode, Nat. Commun., 9(2018), No. 1, art. No. 3656. doi: 10.1038/s41467-018-06077-5
[27]	J.L. Lang, Y.Z. Long, J.L. Qu, et al., One-pot solution coating of high quality LiF layer to stabilize Li metal anode, Energy Storage Mater., 16(2019), p. 85. doi: 10.1016/j.ensm.2018.04.024
[28]	W. Liu, J.X. Li, H.Y. Xu, J. Li, and X.P. Qiu, Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating, Int. J. Miner. Metall. Mater., 29(2022), No. 5, p. 917. doi: 10.1007/s12613-022-2483-7
[29]	S.S. Liu, Y.L. Ma, J.J. Wang, et al., Regulating Li deposition by constructing homogeneous LiF protective layer for high-performance Li metal anode, Chem. Eng. J., 427(2022), art. No. 131625. doi: 10.1016/j.cej.2021.131625
[30]	Q.L. Zhang, J. Pan, P. Lu, et al., Synergetic effects of inorganic components in solid electrolyte interphase on high cycle efficiency of lithium ion batteries, Nano Lett., 16(2016), No. 3, p. 2011. doi: 10.1021/acs.nanolett.5b05283
[31]	L. Fan, H.L. Zhuang, L.N. Gao, Y.Y. Lu, and L.A. Archer, Regulating Li deposition at artificial solid electrolyte interphases, J. Mater. Chem. A, 5(2017), No. 7, p. 3483. doi: 10.1039/C6TA10204B
[32]	D.C. Lin, Y.Y. Liu, W. Chen, et al., Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent Freon, Nano Lett., 17(2017), No. 6, p. 3731. doi: 10.1021/acs.nanolett.7b01020
[33]	Y. Xu, Y.W. Sun, Y. Sun, H.Y. Fang, Y. Jiang, and B. Zhao, Theoretical calculation study on the electrochemical properties of lithium halide-based artificial SEI films for lithium metal anodes, Surf. Interfaces, 44(2024), art. No. 103768. doi: 10.1016/j.surfin.2023.103768
[34]	B. Ouyang, N. Artrith, Z.Y. Lun, et al., Effect of fluorination on lithium transport and short-range order in disordered-rocksalt-type lithium-ion battery cathodes, Adv. Energy Mater., 10(2020), No. 10, art. No. 1903240. doi: 10.1002/aenm.201903240
[35]	Z. Liu, Y. Qi, Y.X. Lin, L. Chen, P. Lu, and L.Q. Chen, Interfacial study on solid electrolyte interphase at Li metal anode: mplication for Li dendrite growth, J. Electrochem. Soc., 163(2016), No. 3, art. No. A592. doi: 10.1149/2.0151605jes
[36]	M.F. He, R. Guo, G.M. Hobold, H.N. Gao, and B.M. Gallant, The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium, Proc. Natl. Acad. Sci., 117(2020), No. 1, p. 73. doi: 10.1073/pnas.1911017116
[37]	L. Chen, K.S. Chen, X.J. Chen, et al., Novel ALD chemistry enabled low-temperature synthesis of lithium fluoride coatings for durable lithium anodes, ACS Appl. Mater. Interfaces, 10(2018), No. 32, p. 26972. doi: 10.1021/acsami.8b04573
[38]	X.L. Fan, X. Ji, F.D. Han, et al., Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery, Sci. Adv., 4(2018), No. 12, art. No. eaau9245. doi: 10.1126/sciadv.aau9245
[39]	Y.X. Yuan, F. Wu, G.H. Chen, Y. Bai, and C. Wu, Porous LiF layer fabricated by a facile chemical method toward dendrite-free lithium metal anode, J. Energy Chem., 37(2019), p. 197. doi: 10.1016/j.jechem.2019.03.014
[40]	C. Monroe and J. Newman, The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces, J. Electrochem. Soc., 152(2005), No. 2, art. No. A396. doi: 10.1149/1.1850854
[41]	S. Yu, R.D. Schmidt, R. Garcia-Mendez, et al., Elastic properties of the solid electrolyte Li₇La₃Zr₂O₁₂(LLZO), Chem. Mater., 28(2016), No. 1, p. 197. doi: 10.1021/acs.chemmater.5b03854
[42]	J. Ko and Y.S. Yoon, Lithium fluoride layer formed by thermal evaporation for stable lithium metal anode in rechargeable batteries, Thin Solid Films, 673(2019), p. 119. doi: 10.1016/j.tsf.2019.01.048
[43]	Y.L. Wang, F.M. Liu, G.L. Fan, et al., Electroless formation of a fluorinated Li/Na hybrid interphase for robust lithium anodes, J. Am. Chem. Soc., 143(2021), No. 7, p. 2829. doi: 10.1021/jacs.0c12051
[44]	S.F. Liu, X. Ji, J. Yue, et al., High interfacial-energy interphase promoting safe lithium metal batteries, J. Am. Chem. Soc., 142(2020), No. 5, p. 2438. doi: 10.1021/jacs.9b11750
[45]	F.A. Soto, P.F. Yan, M.H. Engelhard, et al., Tuning the solid electrolyte interphase for selective Li- and Na-ion storage in hard carbon, Adv. Mater., 29(2017), No. 18, art. No. 1606860. doi: 10.1002/adma.201606860
[46]	J. Xie, L. Liao, Y.J. Gong, et al., Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode, Sci. Adv., 3(2017), No. 11, art. No. eaao3170. doi: 10.1126/sciadv.aao3170
[47]	X.W. Shen, Y.T. Li, T. Qian, et al., Lithium anode stable in air for low-cost fabrication of a dendrite-free lithium battery, Nat. Commun., 10(2019), art. No. 900. doi: 10.1038/s41467-019-08767-0
[48]	Q. Jin, K.X. Zhao, J.H. Wang, et al., Modulating electron conducting properties at lithium anode interfaces for durable lithium–sulfur batteries, ACS Appl. Mater. Interfaces, 14(2022), No. 48, p. 53850. doi: 10.1021/acsami.2c16362
[49]	J. Yang, J.M. Hou, Z.X. Fang, et al., Simultaneously in situ fabrication of lithium fluoride and sulfide enriched artificial solid electrolyte interface facilitates high stable lithium metal anode, Chem. Eng. J., 433(2022), art. No. 133193. doi: 10.1016/j.cej.2021.133193
[50]	Z.D. Li, L.Y. Huai, S. Li, et al., Insight into bulk charge transfer of lithium metal anodes by synergism of nickel seeding and LiF–Li₃N–Li₂S co-doped interphase, Energy Storage Mater., 37(2021), p. 491. doi: 10.1016/j.ensm.2021.02.033
[51]	Z. Peng, N. Zhao, Z.G. Zhang, et al., Stabilizing Li/electrolyte interface with a transplantable protective layer based on nanoscale LiF domains, Nano Energy, 39(2017), p. 662. doi: 10.1016/j.nanoen.2017.07.052
[52]	X. Ji, S. Hou, P.F. Wang, et al., Solid-state electrolyte design for lithium dendrite suppression, Adv. Mater.,32(2020), No. 46, art. No.2002741.
[53]	A.J. Hu, W. Chen, X.C. Du, et al., An artificial hybrid interphase for an ultrahigh-rate and practical lithium metal anode, Energy Environ. Sci., 14(2021), No. 7, p. 4115. doi: 10.1039/D1EE00508A
[54]	J.Y. Wei, X.Q. Zhang, L.P. Hou, et al., Shielding polysulfide intermediates by an organosulfur-containing solid electrolyte interphase on the lithium anode in lithium–sulfur batteries, Adv. Mater., 32(2020), No. 37, art. No. 2003012. doi: 10.1002/adma.202003012
[55]	Y.P. Sun, Y. Zhao, J.W. Wang, et al., A novel organic “polyurea” thin film for ultralong-life lithium–metal anodes via molecular-layer deposition, Adv. Mater., 31(2019), No. 4, art. No. 1806541. doi: 10.1002/adma.201806541
[56]	S.X. Deng, Y.P. Sun, X. Li, et al., Eliminating the detrimental effects of conductive agents in sulfide-based solid-state batteries, ACS Energy Lett., 5(2020), No. 4, p. 1243. doi: 10.1021/acsenergylett.0c00256
[57]	C. Yan, X.B. Cheng, Y. Tian, et al., Dual-layered film protected lithium metal anode to enable dendrite-free lithium deposition, Adv. Mater., 30(2018), No. 25, art. No. 1707629. doi: 10.1002/adma.201707629
[58]	R. Xu, X.Q. Zhang, X.B. Cheng, et al., Artificial soft-rigid protective layer for dendrite-free lithium metal anode, Adv. Funct. Mater., 28(2018), No. 8, art. No. 1705838. doi: 10.1002/adfm.201705838
[59]	S.G. Guo, N. Piao, L. Wang, et al., PVDF–HFP/LiF composite interfacial film to enhance the stability of Li–metal anodes, ACS Appl. Energy Mater., 3(2020), No. 7, p. 7191. doi: 10.1021/acsaem.0c01232
[60]	S.M. Xu, H. Duan, J.L. Shi, et al. , In situ fluorinated solid electrolyte interphase towards long-life lithium metal anodes, Nano Res., 13(2020), No. 2, p. 430. doi: 10.1007/s12274-020-2625-z
[61]	C.W. Ma, G. Mu, H.J. Lv, et al. , In situ-formed flexible three-dimensional honeycomb-like film for a LiF/Li₃N-enriched hybrid organic–inorganic interphase on the Li metal anode, Mater. Chem. Front., 5(2021), No. 13, p. 5082. doi: 10.1039/D1QM00185J
[62]	C.Y. Fu and C. Battaglia, Polymer–inorganic nanocomposite coating with high ionic conductivity and transference number for a stable lithium metal anode, ACS Appl. Mater. Interfaces, 12(2020), No. 37, p. 41620. doi: 10.1021/acsami.0c13485
[63]	S.F. Liu, X.H. Xia, S.J. Deng, et al. , In situ solid electrolyte interphase from spray quenching on molten Li: A new way to construct high-performance lithium–metal anodes, Adv. Mater., 31(2019), No. 3, art. No. e1806470. doi: 10.1002/adma.201806470
[64]	N.W Li, Y.X Yin, C.P Yang, and Y.G Guo, An artificial solid electrolyte interphase layer for stable lithium metal anodes, Adv. Mater., 28(2016), No. 9, p. 1853. doi: 10.1002/adma.201504526
[65]	Q.F. Yang, J.L. Hu, J.W. Meng, and C.L. Li, C–F-rich oil drop as a non-expendable fluid interface modifier with low surface energy to stabilize a Li metal anode, Energy Environ. Sci., 14(2021), No. 6, p. 3621. doi: 10.1039/D0EE03952G
[66]	Y. Gao, Z.F. Yan, J.L. Gray, et al., Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions, Nat. Mater., 18(2019), No. 4, p. 384. doi: 10.1038/s41563-019-0305-8
[67]	C.Z. Zhao, X.Q. Zhang, X.B. Cheng, et al., An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes, Proc. Natl. Acad. Sci., 114(2017), No. 42, p. 11069. doi: 10.1073/pnas.1708489114
[68]	S. Wenzel, S. Randau, T. Leichtweiß, et al., Direct observation of the interfacial instability of the fast ionic conductor Li₁₀GeP₂S₁₂ at the lithium metal anode, Chem. Mater., 28(2016), No. 7, p. 2400. doi: 10.1021/acs.chemmater.6b00610
[69]	X.Q. Yu, J.P. Sun, K. Tang, et al., Reversible lithium storage in LiF/Ti nanocomposites, Phys. Chem. Chem. Phys., 11(2009), No. 41, art. No. 9497. doi: 10.1039/b908149f
[70]	J.H. Yan, J.Y. Yu, and B. Ding, Mixed ionic and electronic conductor for Li–metal anode protection, Adv. Mater., 30(2018), No. 7, art. No. 1705105. doi: 10.1002/adma.201705105
[71]	J. Maier, Defect chemistry in heterogeneous systems, Solid State Ionics, 75(1995), p. 139. doi: 10.1016/0167-2738(94)00222-E
[72]	C. Yan, X.B. Cheng, Y.X. Yao, et al., An armored mixed conductor interphase on a dendrite-free lithium–metal anode, Adv. Mater., 30(2018), No. 45, art. No. 1804461. doi: 10.1002/adma.201804461
[73]	T. Lapp, Ionic conductivity of pure and doped Li₃N, Solid State Ionics, 11(1983), No. 2, p. 97. doi: 10.1016/0167-2738(83)90045-0
[74]	U.V. Alpen, A. Rabenau, and G.H. Talat, Ionic conductivity in Li₃N single crystals, Appl. Phys. Lett., 30(1977), No. 12, p. 621. doi: 10.1063/1.89283
[75]	J.R. Li, H. Su, M. Li, et al., Fluorinated interface layer with embedded zinc nanoparticles for stable lithium–metal anodes, ACS Appl. Mater. Interfaces, 13(2021), No. 15, p. 17690. doi: 10.1021/acsami.1c02868
[76]	P.L. Li, W.L. Feng, X.L. Dong, Y.G. Wang, and Y.Y. Xia, A new strategy of constructing a highly fluorinated solid–electrolyte interface towards high-performance lithium anode, Adv. Mater. Interfaces, 7(2020), No. 11, art. No. 2000154. doi: 10.1002/admi.202000154
[77]	L.W. Tan, C.L. Wei, Y.C. Zhang, Y.L. An, S.L. Xiong, and J.K. Feng, LiF-rich and self-repairing interface induced by MgF₂ engineered separator enables dendrite-free lithium metal batteries, Chem. Eng. J., 442(2022), art. No. 136243. doi: 10.1016/j.cej.2022.136243
[78]	W.W. Hou, S.B. Li, J.X. Liang, B. Yuan, and R.Z. Hu, Lithiophilic NiF₂ coating inducing LiF-rich solid electrolyte interphase by a novel NF₃ plasma treatment for highly stable Li metal anode, Electrochim. Acta, 402(2022), art. No. 139561. doi: 10.1016/j.electacta.2021.139561
[79]	Z. Peng, J.H. Song, L.Y. Huai, et al., Enhanced stability of Li metal anodes by synergetic control of nucleation and the solid electrolyte interphase, Adv. Energy Mater., 9(2019), No. 42, art. No. 1901764. doi: 10.1002/aenm.201901764
[80]	H.Y. Zhang, S.L. Ju, G.L. Xia, D.L. Sun, and X.B. Yu, Dendrite-free Li–metal anode enabled by dendritic structure, Adv. Funct. Mater., 31(2021), No. 16, art. No. 2009712. doi: 10.1002/adfm.202009712
[81]	W. Guo, Q. Han, J.R. Jiao, et al. , In situ construction of robust biphasic surface layers on lithium metal for lithium–sulfide batteries with long cycle life, Angew. Chem. Int. Ed., 60(2021), No. 13, p. 7267. doi: 10.1002/anie.202015049
[82]	X.Y. Xu, Y.Y. Liu, J.Y. Hwang, et al., Role of Li-ion depletion on electrode surface: Underlying mechanism for electrodeposition behavior of lithium metal anode, Adv. Energy Mater., 10(2020), No. 44, art. No. 2002390. doi: 10.1002/aenm.202002390
[83]	L.F. Ai, Z.Y. Chen, S.P. Li, et al., Stabilizing Li plating by a fluorinated hybrid protective layer, ACS Appl. Energy Mater., 4(2021), No. 12, p. 14407. doi: 10.1021/acsaem.1c03078
[84]	L. Gan, K. Wang, Y.Y. Liu, et al., Dendrite-free Li-metal anode via a dual-function protective interphase layer for stable Li–metal pouch cell, Sustain. Mater. Technol., 36(2023), art. No. e00585.
[85]	A.C. Balazs, T. Emrick, and T.P. Russell, Nanoparticle polymer composites: Where two small worlds meet?, Science, 314(2006), No. 5802, p. 1107. doi: 10.1126/science.1130557
[86]	R. Krishnamoorti, Strategies for dispersing nanoparticles in polymers, MRS Bull., 32(2007), No. 4, p. 341. doi: 10.1557/mrs2007.233
[87]	J.L. Jiang, Y.H. Ou, S.Y. Lu, et al. , In-situ construction of Li–Mg/LiF conductive layer to achieve an intimate lithium-garnet interface for all-solid-state Li metal battery, Energy Storage Mater., 50(2022), p. 810. doi: 10.1016/j.ensm.2022.06.011
[88]	R. Pathak, K. Chen, A. Gurung, et al., Fluorinated hybrid solid–electrolyte-interphase for dendrite-free lithium deposition, Nat. Commun., 11(2020), No. 1, art. No. 93. doi: 10.1038/s41467-019-13774-2
[89]	B.K. Hu, W. Yu, B.Q. Xu, et al., An in situ-formed mosaic Li₇Sn₃/LiF interface layer for high-rate and long-life garnet-based lithium metal batteries, ACS Appl. Mater. Interfaces, 11(2019), No. 38, p. 34939. doi: 10.1021/acsami.9b10534
[90]	H.S. Wang, D.C. Lin, Y.Y. Liu, Y.Z. Li, and Y. Cui, Ultrahigh-current density anodes with interconnected Li metal reservoir through overlithiation of mesoporous AlF₃ framework, Sci. Adv., 3(2017), No. 9, art. No. e1701301. doi: 10.1126/sciadv.1701301
[91]	T.R. Wang, J. Duan, B. Zhang, et al., A self-regulated gradient interphase for dendrite-free solid-state Li batteries, Energy Environ. Sci., 15(2022), No. 3, p. 1325. doi: 10.1039/D1EE03604A
[92]	Z.S. Wang, Z.M. Xu, X.J. Jin, et al., Dendrite-free and air-stable lithium metal batteries enabled by electroless plating with aluminum fluoride, J. Mater. Chem. A, 8(2020), No. 18, p. 9218. doi: 10.1039/D0TA02410D
[93]	M.K. Song, J.H. Yim, S.H. Baek, and J.W. Lee, A carbon cloth with a coating layer containing aluminum fluoride as an interlayer for lithium metal batteries, Appl. Surf. Sci., 588(2022), art. No. 152935. doi: 10.1016/j.apsusc.2022.152935
[94]	L.L. Wang, S.Y. Fu, T. Zhao, et al. , In situ formation of a LiF and Li–Al alloy anode protected layer on a Li metal anode with enhanced cycle life, J. Mater. Chem. A, 8(2020), No. 3, p. 1247. doi: 10.1039/C9TA10965J
[95]	F. Li, Y.H. Tan, Y.C. Yin, et al., A fluorinated alloy-type interfacial layer enabled by metal fluoride nanoparticle modification for stabilizing Li metal anodes, Chem. Sci., 10(2019), No. 42, p. 9735. doi: 10.1039/C9SC01845J