A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li4Ti5O12 (LTO) electrode and ceramic/polymer composite electrolyte with a little liquid electrolyte (10 µL/cm2) to provide the outstanding electrochemical stability and better normal interface contact. Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscopy (STEM), Transmission Electron Microscopy (TEM), and Energy Dispersive Spectrometer (EDS) were used to analyze the structural evolution and performance of plasma sprayed amorphous LTO electrode and ceramic/polymer composite electrolyte before and after electrochemical experiments. By comparing the electrochemical performance of the amorphous LTO electrode and the traditional LTO electrode, the electrochemical behavior of different electrodes is studied. The results show that plasma spraying can prepare an amorphous LTO electrode coating of about 8 µm. After 200 electrochemical cycles, the structure of the electrode evolved, and the inside of the electrode fractured and cracks expanded, because of recrystallization at the interface between the rich fluorine compounds and the amorphous LTO electrode. Similarly, the ceramic/polymer composite electrolyte has undergone structural evolution after 200 test cycles. The electrochemical cycle results show that the cycle stability, capacity retention rate, coulomb efficiency, and internal impedance of amorphous LTO electrode are better than traditional LTO electrode. This innovative and facile quasi-solid-state strategy is aimed to promote the intrinsic safety and stability of working lithium battery, shedding light on the development of next-generation high-performance solid-state lithium batteries.
Chen Y, Wen KH, Chen TH, et al. Recent progress in all-solid-state lithium batteries: The emerging strategies for advanced electrolytes and their interfaces. Energy Storage Mater 2020, 31: 401–433.
Pat S, Özen S, Yudar HH, et al. The transparent all-solidstate rechargeable micro-battery manufacturing by RF magnetron sputtering. J Alloys Compd 2017, 713: 64–68.
Matsuda Y, Kuwata N, Kawamura J. Thin-film lithium batteries with 0.3–30 µm thick LiCoO2 films fabricated by high-rate pulsed laser deposition. Solid State Ionics 2018, 320: 38–44.
Choi M, Lee SH, Jung YI, et al. The high capacity and cycle stability of NiFe2O4 thin film prepared by E-beam evaporation method for lithium ion batteries. J Alloys Compd 2017, 729: 802–808.
Shi HB, Zhang H, Li XX, et al. In situ fabrication of dual coating structured SiO/1D-C/a-C composite as highperformance lithium ion battery anode by fluidized bed chemical vapor deposition. Carbon 2020, 168: 113–124.
Chen T, Meng FB, Zhang ZW, et al. Stabilizing lithium metal anode by molecular beam epitaxy grown uniform and ultrathin bismuth film. Nano Energy 2020, 76: 105068.
Choi Y, Kim JI, Moon J, et al. Electron beam induced strong organic/inorganic grafting for thermally stable lithium-ion battery separators. Appl Surf Sci 2018, 444: 339–344.
Nuroniah I, Priyono S, Subhan A, et al. Synthesis and characterization of Al-doped Li4Ti5O12 with sol gel method for anode material lithium ion battery. Mater Today: Proc 2019, 13: 65–70.
Xue B, Wang K, Tan Y, et al. Studies on performance of SiO addition to Li4Ti5O12 as anode material for lithium-ion batteries. Chem Phys Lett 2019, 730: 623–629.
Wang Y, Zhu WJ. Micro/nano-structured Li4Ti5O12 as high rate anode material for lithium ion batteries. Solid State Ionics 2020, 349: 115297.
Matsuyama T, Sakuda A, Hayashi A, et al. Electrochemical properties of all-solid-state lithium batteries with amorphous titanium sulfide electrodes prepared by mechanical milling. J Solid State Electrochem 2013, 17: 2697–2701.
Matsuyama T, Sakuda A, Hayashi A, et al. Preparation of amorphous TiSx thin film electrodes by the PLD method and their application to all-solid-state lithium secondary batteries. J Mater Sci 2012, 47: 6601–6606.
Hayashi A, Konishi T, Tadanaga K, et al. All-solid-state rechargeable lithium batteries using SnX-P2X5 (X = S and O) amorphous negative electrodes. Res Chem Intermed 2006, 32: 497–506.
Chen LB, Xie JY, Yu HC, et al. An amorphous Si thin film anode with high capacity and long cycling life for lithium ion batteries. J Appl Electrochem 2009, 39: 1157–1162.
Meng RJ, Hou HY, Liu XX, et al. Binder-free combination of amorphous TiO2 nanotube arrays with highly conductive Cu bridges for lithium ion battery anode. Ionics 2016, 22: 1527–1532.
Hayashi T, Matsuda Y, Kuwata N, et al. High-power durability of LiCoO2 thin film electrode modified with amorphous lithium tungsten oxide. J Power Sources 2017, 354: 41–47.
Lin ZY, Guo XW, Yu HJ. Amorphous modified silyl-terminated 3D polymer electrolyte for high-performance lithium metal battery. Nano Energy 2017, 41: 646–653.
Wang LP, Wang QJ, Jia WS, et al. Li metal coated with amorphous Li3PO4 via magnetron sputtering for stable and long-cycle life lithium metal batteries. J Power Sources 2017, 342: 175–182.
Zhao Y, Yan JH, Cai WP, et al. Elastic and well-aligned ceramic LLZO nanofiber based electrolytes for solid-state lithium batteries. Energy Storage Mater 2019, 23: 306–313.
Yang ZL, Yuan HY, Zhou CJ, et al. Facile interfacial adhesion enabled LATP-based solid-state lithium metal battery. Chem Eng J 2020, 392: 123650.
Cheng J, Hou GM, Sun Q, et al. Cold-pressing PEO/LAGP composite electrolyte for integrated all-solid-state lithium metal battery. Solid State Ionics 2020, 345: 115156.
Zhang BH, Liu YL, Liu J, et al. “Polymer-in-ceramic” based poly(ε-caprolactone)/ceramic composite electrolyte for all-solid-state batteries. J Energy Chem 2021, 52: 318–325.
Liang XH, Wang YT, Zhang XF, et al. Performance study of a Li4Ti5O12 electrode for lithium batteries prepared by atmospheric plasma spraying. Ceram Int 2019, 45: 23750–23755.
Umirov N, Yamada Y, Munakata H, et al. Analysis of intrinsic properties of Li4Ti5O12 using single-particle technique. J Electroanal Chem 2019, 855: 113514.
Sun RB, Gao JY, Wu G, et al. Amorphous metal oxide nanosheets featuring reversible structure transformations as sodium-ion battery anodes. Cell Rep Phys Sci 2020, 1: 100118.
Yun YS, Jin HJ. Electrochemical performance of heteroatom-enriched amorphous carbon with hierarchical porous structure as anode for lithium-ion batteries. Mater Lett 2013, 108: 311–315.
Zhang BY, Yang GJ, Li CX, et al. Non-parabolic isothermal oxidation kinetics of low pressure plasma sprayed MCrAlY bond coat. Appl Surf Sci 2017, 406: 99–109.
Hayashi T, Miyazaki T, Matsuda Y, et al. Effect of lithium-ion diffusibility on interfacial resistance of LiCoO2 thin film electrode modified with lithium tungsten oxides. J Power Sources 2016, 305: 46–53.
Bhat MY, Yadav N, Hashmi SA. A high performance flexible gel polymer electrolyte incorporated with suberonitrile as additive for quasi-solid carbon supercapacitor. Mat Sci Eng B 2020, 262: 114721.
Guo QP, Han Y, Wang H, et al. New class of LAGP-based solid polymer composite electrolyte for efficient and safe solid-state lithium batteries. ACS Appl Mater Interfaces 2017, 9: 41837–41844.
Li A, Liao X, Zhang H, et al. Nacre-inspired composite electrolytes for load-bearing solid-state lithium-metal batteries. Adv Mater 2019, 32: 1905517.
Yu XW, Manthiram A. A review of composite polymer-ceramic electrolytes for lithium batteries. Energy Storage Mater 2021, 34: 282–300.
This work was supported by the Fund Project of the GDAS Special Project of Science and Technology Development, Guangdong Academy of Sciences Program (No. 2020GDASYL-20200104030); the Innovation Project of Guangxi University of Science and Technology Graduate Education (No. YCSW2020217); Guangxi Innovation Driven Development Project (No. AA18242036-2); Innovation Team Project of Guangxi University of Science and Technology (No. 3); and the Fund Project of the Key Lab of Guangdong for Modern Surface Engineering Technology (No. 2018KFKT01).
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Wu, X., Liang, X., Zhang, X. et al. Structural evolution of plasma sprayed amorphous Li4Ti5O12 electrode and ceramic/polymer composite electrolyte during electrochemical cycle of quasi-solid-state lithium battery. J Adv Ceram 10, 347–354 (2021). https://doi.org/10.1007/s40145-020-0447-9
- plasma spraying
- Li4Ti5O12 (LTO) electrode
- ceramic/polymer composite electrolyte
- electrochemical cycle
- quasi-solid-state lithium battery