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.
| [1] |
Placke T, Kloepsch R, Dühnen S, Winter M. Lithium ion, lithium metal, and alternative rechargeable battery technologies: The odyssey for high energy density. J. Solid State Electro-chem.. 2017, 21(7): 1939
|
| [2] |
Grande L, Paillard E, Hassoun J, et al. . The lithium/air battery: Still an emerging system or a practical reality?. Adv. Mater.. 2015, 27(5): 784
|
| [3] |
Albertus P, Babinec S, Litzelman S, Newman A. Status and challenges in enabling the lithium metal electrode for high-energy and low-cost rechargeable batteries. Nat. Energy. 2018, 3: 16
|
| [4] |
Heine J, Hilbig P, Qi X, Niehoff P, Winter M, Bieker P. Fluoroethylene carbonate as electrolyte additive in tetraethyl-ene glycol dimethyl ether based electrolytes for application in lithium ion and lithium metal batteries. J. Electrochem. Soc.. 2015, 162(6): A1094
|
| [5] |
Cao KZ, Wang ST, He YN, Ma JH, Yue ZW, Liu HQ. Constructing Al@C-Sn pellet anode without passivation layer for lithium-ion battery. Int. J. Miner. Metall. Mater.. 2024, 31(3): 552
|
| [6] |
Wei T, Zhang Q, Wang SJ, et al. . A gel polymer electrolyte with IL@UiO-66-NH2 as fillers for high-performance all-solidstate lithium metal batteries. Int. J. Miner. Metall. Mater.. 2023, 30(10): 1897
|
| [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.
|
| [8] |
Chen XL, Gong YD, Li X, Zhan F, Liu XH, Ma JM. Perspective on low-temperature electrolytes for LiFePO4-based lithium-ion batteries. Int. J. Miner. Metall. Mater.. 2023, 30(1): 1
|
| [9] |
Cheng XB, Huang JQ, Zhang Q. Review—Li metal anode in working lithium-sulfur batteries. J. Electrochem. Soc.. 2017, 165(1): A6058
|
| [10] |
Cheng XB, Yan C, Zhang XQ, Liu H, Zhang Q. Electronic and ionic channels in working interfaces of lithium metal anodes. ACS Energy Lett.. 2018, 3(7): 1564
|
| [11] |
Lu YY, Tu ZY, Archer LA. Stable lithium electrodeposition in liquid and nanoporous solid electrolytes. Nat. Mater.. 2014, 13(10): 961
|
| [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.
|
| [13] |
Peled E. Film forming reaction at the lithium/electrolyte interface. J. Power Sources. 1983, 9(3): 253
|
| [14] |
Zhou YF, Su M, Yu XF, et al. . Real-time mass spectromet-ric characterization of the solid-electrolyte interphase of a lithium-ion battery. Nat. Nanotechnol.. 2020, 15(3): 224
|
| [15] |
Nazri G, Muller RH. Composition of surface layers on Li electrodes in PC, LiClO4 of very low water content. J. Electro-chem. Soc.. 1985, 132(9): 2050
|
| [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.
|
| [17] |
Garreau M. Cyclability of the lithium electrode. J. Power Sources. 1987, 20(1–2): 9
|
| [18] |
Thevenin J. Passivating films on lithium electrodes. An approach by means of electrode impedance spectroscopy. J. Power Sources. 1985, 14(1–3): 45
|
| [19] |
Thevenin JG, Muller RH. Impedance of lithium electrodes in a propylene carbonate electrolyte. J. Electrochem. Soc.. 1987, 134(2): 273
|
| [20] |
Zhang SS, Xu K, Jow TR. Enhanced performance of Li-ion cell with LiBF4-PC based electrolyte by addition of small amount of LiBOB. J. Power Sources. 2006, 156(2): 629
|
| [21] |
G.W. Zheng and T. Wei, Batteries: Just a spoonful of LiPF6, Nat. Energy, 2(2017), No. 3, art. No. 17029.
|
| [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.
|
| [23] |
Ko J, Yoon YS. Recent progress in LiF materials for safe lithium metal anode of rechargeable batteries: Is LiF the key to commercializing Li metal batteries?. Ceram. Int.. 2019, 45(1): 30
|
| [24] |
Li T, Zhang XQ, Shi P, Zhang Q. Fluorinated solid-electrolyte interphase in high-voltage lithium metal batteries. Joule. 2019, 3(11): 2647
|
| [25] |
Zhao J, Liao L, Shi FF, et al. . Surface fluorination of reactive battery anode materials for enhanced stability. J. Am. Chem. Soc.. 2017, 139(33): 11550
|
| [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.
|
| [27] |
Lang JL, Long YZ, Qu JL, et al. . One-pot solution coating of high quality LiF layer to stabilize Li metal anode. Energy Storage Mater.. 2019, 16: 85
|
| [28] |
Liu W, Li JX, Xu HY, Li J, Qiu XP. Stabilized cobalt-free lithium-rich cathode materials with an artificial lithium fluoride coating. Int. J. Miner. Metall. Mater.. 2022, 29(5): 917
|
| [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.
|
| [30] |
Zhang QL, Pan J, Lu P, et al. . Synergetic effects of inorganic components in solid electrolyte interphase on high cycle efficiency of lithium ion batteries. Nano Lett.. 2016, 16(3): 2011
|
| [31] |
Fan L, Zhuang HL, Gao LN, Lu YY, Archer LA. Regulating Li deposition at artificial solid electrolyte interphases. J. Mater. Chem A. 2017, 5(7): 3483
|
| [32] |
Lin DC, Liu YY, Chen W, et al. . Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent Freon. Nano Lett.. 2017, 17(6): 3731
|
| [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.
|
| [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.
|
| [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.
|
| [36] |
He MF, Guo R, Hobold GM, Gao HN, Gallant BM. The intrinsic behavior of lithium fluoride in solid electrolyte interphases on lithium. Proc. Natl. Acad. Sci.. 2020, 117(1): 73
|
| [37] |
Chen L, Chen KS, Chen XJ, et al. . Novel ALD chemistry enabled low-temperature synthesis of lithium fluoride coatings for durable lithium anodes. ACS Appl. Mater. Interfaces. 2018, 10(32): 26972
|
| [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.
|
| [39] |
Yuan YX, Wu F, Chen GH, Bai Y, Wu C. Porous LiF layer fabricated by a facile chemical method toward dendrite-free lithium metal anode. J. Energy Chem.. 2019, 37: 197
|
| [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.
|
| [41] |
Yu S, Schmidt RD, Garcia-Mendez R, et al. . Elastic properties of the solid electrolyte Li7La3Zr2O12(LLZO). Chem. Mater.. 2016, 28(1): 197
|
| [42] |
Ko J, Yoon YS. Lithium fluoride layer formed by thermal evaporation for stable lithium metal anode in rechargeable batteries. Thin Solid Films. 2019, 673: 119
|
| [43] |
Wang YL, Liu FM, Fan GL, et al. . Electroless formation of a fluorinated Li/Na hybrid interphase for robust lithium anodes. J. Am Chem Soc.. 2021, 143(7): 2829
|
| [44] |
Liu SF, Ji X, Yue J, et al. . High interfacial-energy interphase promoting safe lithium metal batteries. J. Am. Chem. Soc.. 2020, 142(5): 2438
|
| [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.
|
| [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.
|
| [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.
|
| [48] |
Jin Q, Zhao KX, Wang JH, et al. . Modulating electron conducting properties at lithium anode interfaces for durable lithium-sulfur batteries. ACS Appl. Mater. Interfaces. 2022, 14(48): 53850
|
| [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.
|
| [50] |
Li ZD, Huai LY, Li S, 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.. 2021, 37: 491
|
| [51] |
Peng Z, Zhao N, Zhang ZG, et al. . Stabilizing Li/electrolyte interface with a transplantable protective layer based on nano-scale LiF domains. Nano Energy. 2017, 39: 662
|
| [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] |
Hu AJ, Chen W, Du XC, et al. . An artificial hybrid interphase for an ultrahigh-rate and practical lithium metal anode. Energy Environ. Sci.. 2021, 14(7): 4115
|
| [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.
|
| [55] |
Y.P. Sun, Y. Zhao, J.W. Wang, et al., A novel organic “poly-urea” thin film for ultralong-life lithium-metal anodes via molecular-layer deposition, Adv. Mater., 31(2019), No. 4, art. No. 1806541.
|
| [56] |
Deng SX, Sun YP, Li X, et al. . Eliminating the detrimental effects of conductive agents in sulfide-based solid-state batteries. ACS Energy Lett.. 2020, 5(4): 1243
|
| [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.
|
| [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.
|
| [59] |
Guo SG, Piao N, Wang L, et al. . PVDF-HFP/LiF composite interfacial film to enhance the stability of Li-metal anodes. ACS Appl. Energy Mater.. 2020, 3(7): 7191
|
| [60] |
Xu SM, Duan H, Shi JL, et al. . In situ fluorinated solid electrolyte interphase towards long-life lithium metal anodes. Nano Res.. 2020, 13(2): 430
|
| [61] |
Ma CW, Mu G, Lv HJ, 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.. 2021, 5(13): 5082
|
| [62] |
Fu CY, Battaglia C. Polymer-inorganic nanocomposite coating with high ionic conductivity and transference number for a stable lithium metal anode. ACS Appl. Mater. Interfaces. 2020, 12(37): 41620
|
| [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.
|
| [64] |
Li NW, Yin YX, Yang CP, Guo YG. An artificial solid electrolyte interphase layer for stable lithium metal anodes. Adv. Mater.. 2016, 28(9): 1853
|
| [65] |
Yang QF, Hu JL, Meng JW, Li CL. 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.. 2021, 14(6): 3621
|
| [66] |
Gao Y, Yan ZF, Gray JL, et al. . Polymer-inorganic solid-electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Mater.. 2019, 18(4): 384
|
| [67] |
Zhao CZ, Zhang XQ, Cheng XB, et al. . An anion-immobil-ized composite electrolyte for dendrite-free lithium metal anodes. Proc. Natl. Acad. Sci.. 2017, 114(42): 11069
|
| [68] |
Wenzel S, Randau S, Leichtweiß T, et al. . Direct observation of the interfacial instability of the fast ionic conductor Li10GeP2S12 at the lithium metal anode. Chem. Mater.. 2016, 28(7): 2400
|
| [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.
|
| [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.
|
| [71] |
Maier J. Defect chemistry in heterogeneous systems. Solid State Ionics. 1995, 75: 139
|
| [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.
|
| [73] |
Lapp T. Ionic conductivity of pure and doped Li3N. Solid State Ionics. 1983, 11(2): 97
|
| [74] |
Alpen UV, Rabenau A, Talat GH. Ionic conductivity in Li3N single crystals. Appl. Phys. Lett.. 1977, 30(12): 621
|
| [75] |
Li JR, Su H, Li M, et al. . Fluorinated interface layer with embedded zinc nanoparticles for stable lithium-metal anodes. ACS Appl. Mater. Interfaces. 2021, 13(15): 17690
|
| [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.
|
| [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.
|
| [78] |
W.W. Hou, S.B. Li, J.X. Liang, B. Yuan, and R.Z. Hu, Lithio-philic 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.
|
| [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.
|
| [80] |
H.Y. Zhang, S.L. Ju, G.L. Xia, D.L. Sun, and X.B. Yu, Dend-rite-free Li-metal anode enabled by dendritic structure, Adv. Funct. Mater., 31(2021), No. 16, art. No. 2009712.
|
| [81] |
Guo W, Han Q, Jiao JR, 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.. 2021, 60(13): 7267
|
| [82] |
X.Y. Xu, Y.Y. Liu, J.Y. Hwang, et al., Role of Li-ion depletion on electrode surface: Underlying mechanism for electrodepos-ition behavior of lithium metal anode, Adv. Energy Mater., 10(2020), No. 44, art. No. 2002390.
|
| [83] |
Ai LF, Chen ZY, Li SP, et al. . Stabilizing Li plating by a fluorinated hybrid protective layer. ACS Appl. Energy Mater.. 2021, 4(12): 14407
|
| [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] |
Balazs AC, Emrick T, Russell TP. Nanoparticle polymer composites: Where two small worlds meet?. Science. 2006, 314(5802): 1107
|
| [86] |
Krishnamoorti R. Strategies for dispersing nanoparticles in polymers. MRS Bull.. 2007, 32(4): 341
|
| [87] |
Jiang JL, Ou YH, Lu SY, 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.. 2022, 50: 810
|
| [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.
|
| [89] |
Hu BK, Yu W, Xu BQ, 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. 2019, 11(38): 34939
|
| [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.
|
| [91] |
Wang TR, Duan J, Zhang B, et al. . A self-regulated gradient interphase for dendrite-free solid-state Li batteries. Energy Environ. Sci.. 2022, 15(3): 1325
|
| [92] |
Wang ZS, Xu ZM, Jin XJ, et al. . Dendrite-free and air-stable lithium metal batteries enabled by electroless plating with aluminum fluoride. J. Mater. Chem. A. 2020, 8(18): 9218
|
| [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 inter-layer for lithium metal batteries, Appl. Surf. Sci., 588(2022), art. No. 152935.
|
| [94] |
Wang LL, Fu SY, Zhao T, 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. 2020, 8(3): 1247
|
| [95] |
Li F, Tan YH, Yin YC, et al. . A fluorinated alloy-type interfacial layer enabled by metal fluoride nanoparticle modification for stabilizing Li metal anodes. Chem. Sci.. 2019, 10(42): 9735
|
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