Appropriate FeF₂ enhancing interface stability of lithium battery with solid-liquid hybrid electrolyte

Abstract

Solid-state electrolytes (SSEs) have attracted much attention due to their high safety and cycling stability for lithium-ion batteries. However, the high interface impedance between the electrode and the solid-state electrolyte hinders their practical application. In this work, the solid-liquid hybrid electrolyte S-Li_1.3Al_0.3Ti_1.7(PO₄)₃-LE05(S-LATP-LE05) (LATP: Li_1.5Al_0.5Ti_1.5 (PO₄)₃) sheet is prepared by dropping liquid electrolyte (LE) with appropriate FeF₂ into spark plasma sintering S-LATP (solid-liquid hybrid electrolyte), which shows high-density and high-ionic-conductivity (5.78×10⁻⁴ S/cm). When the amount of FeF₂ is 0.5 wt%, the interfacial properties between the anode and electrolyte are improved, and the S-LATP is well protected by LiF-rich (solid electrolyte interface) (SEI) interface in cycling process. The Li∣S-LATP-LE05∣Li symmetric battery and full battery show better electrochemical performance and stability relatively. The overpotential of the Li∣S-LATP-LE05∣Li symmetric battery is smaller and shows more stable electrochemical performance after cycling for 350 h, revealing good compatibility with a lithium metal anode and can inhibit the growth of lithium dendrites effectively. The Li∣S-LATP-LE05∣LiFePO₄ full battery delivers a specific discharge capacity of 160 mA·h/g at 0.2C for 50 cycles. The corresponding coulombic efficiency is about 99.9% and displays better rate performance compared with the battery without FeF₂ LE.

Keywords

Li_1.3Al_0.3Ti_1.7(PO₄)₃ / spark plasma sintering / solid-liquid hybrid electrolyte / interface modification

References

[1] Scrosati B. History of lithium batteries [J]. Journal of Solid State Electrochemistry, 2011, 15(7): 1623-1630.

[2] Lin X-d, Zhou G-d, Liu J-p, et al. . Rechargeable battery electrolytes capable of operating over wide temperature windows and delivering high safety [J]. Advanced Energy Materials, 2020, 10(43): 2001235.

[3] Zhang Y-r, Li F, Cao Y, et al. . Tuning the FEC-related electrolyte solvation structures in ether solvents enables high-performance lithium metal anode [J]. Advanced Functional Materials, 2024, 34(28): 2315527.

[4] Wang N, Luo Z-y, Zhang Q-f, et al. . Succinonitrile broadening the temperature range of Li/CFx primary batteries [J]. Journal of Central South University, 2023, 30(2): 443-453.

[5] Nie Q-n, Luo W-l, Li Y, et al. . Research progress of liquid electrolytes for lithium metal batteries at high temperatures [J]. Small, 2023, 19(46): e2302690.

[6] Randau S, Weber D A, Kötz O, et al. . Benchmarking the performance of all-solid-state lithium batteries [J]. Nature Energy, 2020, 5: 259-270.

[7] Valøen L O, Reimers J N. Transport properties of LiPF₆-based Li-ion battery electrolytes [J]. Journal of the Electrochemical Society, 2005, 152(5): A882.

[8] Etacheri V, Marom R, Elazari R, et al. . Challenges in the development of advanced Li-ion batteries: A review [J]. Energy & Environmental Science, 2011, 4(9): 3243-3262.

[9] Yuan S-y, Ding K, Zeng X-y, et al. . Advanced nonflammable organic electrolyte promises safer Li-metal batteries: From solvation structure perspectives [J]. Advanced Materials, 2023, 35(13): e2206228.

[10] He P-p, Tang Y, Tan Z-l, et al. . Solid-state batteries encounter challenges regarding the interface involving lithium metal [J]. Nano Energy, 2024, 124: 109502.

[11] Wang Z-k, Liu J, Wang M-f, et al. . Toward safer solid-state lithium metal batteries: A review [J]. Nanoscale Advances, 2020, 2(5): 1828-1836.

[12] Yang C-p, Fu K, Zhang Y, et al. . Protected lithium-metal anodes in batteries: From liquid to solid [J]. Advanced Materials, 2017, 29(36): 1701169.

[13] Zhang Z, Han W-qiang. From liquid to solid-state lithium metal batteries: Fundamental issues and recent developments [J]. Nano-Micro Letters, 2023, 16(1): 24.

[14] AN Zhi-tao, LI Wen-tao, PEI Quan, et al. Excellent stable cycle performance of polyethylene oxide-based 3D solid dual-salt composite electrolyte with porous polyimide thin films host [J]. Advanced Materials Technologies, 2024: 2302168. DOI: https://doi.org/10.1002/admt.202302168.

[15] Tan J-w, Ao X, Dai A, et al. . Polycation ionic liquid tailored PEO-based solid polymer electrolytes for high temperature lithium metal batteries [J]. Energy Storage Materials, 2020, 33: 173-180.

[16] Zhang Y-h, Lu M-n, Li Q, et al. . Hybrid lithium salts regulated solid polymer electrolyte for high-temperature lithium metal battery [J]. Journal of Solid State Chemistry, 2022, 310: 123072.

[17] Zhou Z-h, Sun T, Cui J, et al. . A homogenous solid polymer electrolyte prepared by facile spray drying method is used for room-temperature solid lithium metal batteries [J]. Nano Research, 2023, 16(4): 5080-5086.

[18] Yao M, Ruan Q-q, Yu T-h, et al. . Solid polymer electrolyte with in situ generated fast Li⁺ conducting network enable high voltage and dendrite-free lithium metal battery [J]. Energy Storage Materials, 2022, 44: 93-103.

[19] Deck M J, Chien P H, Poudel T P, et al. . Oxygen-induced structural disruption for improved Li⁺ transport and electrochemical stability of Li₃PS₄ [J]. Advanced Energy Materials, 2024, 14(4): 2302785.

[20] Eatmon Y, Stiles J W, Hayashi S, et al. . Air stabilization of Li₇P₃S₁₁ solid-state electrolytes through laser-based processing [J]. Nanomaterials, 2023, 13(15): 2210.

[21] Wan H-l, Liu S-f, Deng T, et al. . Bifunctional interphase-enabled Li₁₀GeP₂S₁₂ electrolytes for lithium-sulfur battery [J]. ACS Energy Letters, 2021, 6(3): 862-868.

[22] Teng Y-n, Guo J-h, Wang Y, et al. . 3D perovskite LLTO nanotubers networks for enhanced Li+ conductivity in composite solid electrolytes [J]. Journal of Materials Science: Materials in Electronics, 2022, 33(33): 25342-25354

[23] Okur F, Zhang H-y, Karabay D T, et al. . Intermediate-stage sintered LLZO scaffolds for Li-garnet solid-state batteries [J]. Advanced Energy Materials, 2023, 13(15): 2203509.

[24] Dewees R, Wang H. Synthesis and properties of NaSICON-type LATP and LAGP solid electrolytes [J]. ChemSusChem, 2019, 12(16): 3713-3725.

[25] Miao S-c, Jia Y, Deng Z-w, et al. . Transition metals for stabilizing lithium metal anode: Advances and perspectives [J]. Tungsten, 2024, 6(1): 212-229.

[26] Dai J-q, Yang C-p, Wang C-w, et al. . Interface engineering for garnet-based solid-state lithium-metal batteries: Materials, structures, and characterization [J]. Advanced Materials, 2018, 30(48): e1802068.

[27] Wang Q-s, Wen Z-y, Jin J, et al. . A gelceramic multi-layer electrolyte for long-life lithium sulfur batteries [J]. Chemical Communications, 2016, 52(8): 1637-1640.

[28] Hu S, Du L-l, Zhang G, et al. . Open-structured nanotubes with three-dimensional ion-accessible pathways for enhanced Li⁺ conductivity in composite solid electrolytes [J]. ACS Applied Materials & Interfaces, 2021, 13(11): 13183-13190.

[29] Liu X-y, Li X-r, Li H-x, et al. . Recent progress of hybrid solid-state electrolytes for lithium batteries [J]. Chemistry, 2018, 24(69): 18293-18306.

[30] Xiao W, Wang J-y, Fan L-l, et al. . Recent advances in Li_1+xAl_xTi_2−x(PO4)₃ solid-state electrolyte for safe lithium batteries [J]. Energy Storage Materials, 2019, 19: 379-400.

[31] Wu F-l, Fang S, Kuenzel M, et al. . Bilayer solid electrolyte enabling quasi-solid-state lithium-metal batteries [J]. Journal of Power Sources, 2023, 557: 232514.

[32] Luo C-w, Yi M, Cao Z-j, et al. . Review of ionic conductivity properties of NASICON type inorganic solid electrolyte LATP [J]. ACS Applied Electronic Materials, 2024, 6(2): 641-657.

[33] Shen S-p, Tang G, Li H-j, et al. . Low-temperature fabrication of NASICON-type LATP with superior ionic conductivity [J]. Ceramics International, 2022, 48(24): 36961-36967.

[34] Aono H, Sugimoto E, Sadaoka Y, et al. . Ionic conductivity of the lithium titanium phosphate (Li_1+xM_xTi_2−x(PO₄)₃, M=Al, Sc, Y, and La) systems [J]. Journal of the Electrochemical Society, 1989, 136(2): 590.

[35] Gu Z-y, Guo J-z, Cao J-m, et al. . An advanced high-entropy fluorophosphate cathode for sodium-ion batteries with increased working voltage and energy density [J]. Advanced Materials, 2022, 34(14): e2110108.

[36] Busche M R, Drossel T, Leichtweiss T, et al. . Dynamic formation of a solid-liquid electrolyte interphase and its consequences for hybrid-battery concepts [J]. Nature Chemistry, 2016, 8(5): 426-434.

[37] Xu Y-d, Tian M, Rong Y, et al. . In situ electrochemical modification of the Li/Li_1.3Al_0.3Ti_1.7(PO₄)₃ interface in solid lithium metal batteries via an electrolyte additive [J]. Journal of Colloid and Interface Science, 2023, 641: 396-403.

[38] Hartmann P, Leichtweiss T, Busche M R, et al. . Degradation of NASICON-type materials in contact with lithium metal: Formation of mixed conducting interphases (MCI) on solid electrolytes [J]. The Journal of Physical Chemistry C, 2013, 117(41): 21064-21074.

[39] Liu Y-l, Sun Q, Zhao Y, et al. . Stabilizing the interface of NASICON solid electrolyte against Li metal with atomic layer deposition [J]. ACS Applied Materials & Interfaces, 2018, 10(37): 31240-31248.

[40] Woolley H M, Vargas-Barbosa N M. Hybrid solid electrolyte-liquid electrolyte systems for (almost) solid-state batteries: Why, how, and where to? [J]. Journal of Materials Chemistry A, 2023, 11(3): 1083-1097.

[41] Wang C-h, Sun Q, Liu Y-l, et al. . Boosting the performance of lithium batteries with solidliquid hybrid electrolytes: Interfacial properties and effects of liquid electrolytes [J]. Nano Energy, 2018, 48: 35-43.

[42] Wang H-s, Huang W-y, Rao R-j, et al. . A fluoride-rich solid-like electrolyte stabilizing lithium metal batteries [J]. Advanced Materials, 2024, 36(19): e2313135.

[43] Ding D-c, Ma H, Tao H-c, et al. . Stabilizing a Li_1.3Al_0.3Ti_1.7(PO₄)₃/Li metal anode interface in solid-state batteries with a LiF/Cu-rich multifunctional interlayer [J]. Chemical Science, 2024, 15(10): 3730-3740.

[44] Liu Q, Yu J-h, Guo W-q, et al. . Boosting the Li∣LAGP interfacial compatibility with trace nonflammable all-fluorinated electrolyte: The role of solid electrolyte interphase [J]. EcoMat, 2023, 5(4): e12322.

[45] Li X, Cong L-n, Ma S-c, et al. . Low resistance and high stable solid – liquid electrolyte interphases enable high-voltage solid-state lithium metal batteries [J]. Advanced Functional Materials, 2021, 31(20): 2010611.

[46] Mukhopadhyay A, Basu B. Consolidation-microstructure-property relationships in bulk nanoceramics and ceramic nanocomposites: A review [J]. International Materials Reviews, 2007, 52(5): 257-288.

[47] Kali R, Mukhopadhyay A. Spark plasma sintered/synthesized dense and nanostructured materials for solid-state Li-ion batteries: Overview and perspective [J]. Journal of Power Sources, 2014, 247: 920-931.

[48] Monroe C, Newman J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces [J]. Journal of the Electrochemical Society, 2005, 152(2): A396.

[49] Zhang Y-l, Wang L, He X-m, et al. . Research status of iron based fluoride cathode materials for lithium ion battery [J]. Energy Storage Science and Technology, 2016, 5(1): 44-57

[50] Fan X-z, Zhang J-h, Yao N, et al. . Directing fluorinated solid electrolyte interphase by solubilizing crystal lithium fluoride in aprotic electrolyte for lithium metal batteries [J]. Advanced Energy Materials, 2024, 14(16): 2303336.

[51] Wu D-x, He J, Liu J-d, et al. . Li₂CO₃/LiF-rich heterostructured solid electrolyte interphase with superior lithiophilic and Li⁺-transferred characteristics via adjusting electrolyte additives [J]. Advanced Energy Materials, 2022, 12(18): 2200337.

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