Citation: Xiaotian ZHU, Fangding HUANG, Wenchang ZHU, Jianqing ZHAO. Layered oxide cathode for sodium-ion batteries: Surface and interface modification and suppressed gas generation effect[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(2): 254-266. doi: 10.11862/CJIC.20240260 shu

Layered oxide cathode for sodium-ion batteries: Surface and interface modification and suppressed gas generation effect

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  • Two surface and interface engineering strategies were developed, i.e., the TiO2@Al2O3 oxide dual coating in a heterostructure and binary Ti#Al based cation co-doping in a gradient surface enrichment to modify NaNi1/3Fe1/3Mn1/3O2 (NFM) cathode material using atomic layered deposition (ALD) and high-temperature annealing runaway temperatures to 285.9 and 289.5 ℃ on the fully-charged condition respectively, corresponding to the increment of 6.1 and 9.7 ℃ compared to the NFM via differential scanning calorimetric (DSC) measurements. In-situ differential electrochemical mass spectrometry (DEMS) was further employed to analyze gas components and corresponding contents in the first two cycles of three different cathodes. As a result, the surface coating benefits from restricting the generation of major H2 components by effectively suppressing the protonation of the electrolyte solvents. By contrast, the lattice doping works for impeding the follow-up reactions of decomposed products from the initial decomposition of electrolytes. process, and their effects on improving electrochemical performance and thermal stability of the NFM cathode, and suppressing gas generation during its sodiation/desodiation were also evaluated. When the capacity reached 60% of the capacity of the second cycle in a voltage range of 2.0-4.0 V (vs Na/Na+) at a high current density of 1C (120 mA· g-1), the surface-coated NFM@TiO2(10)@Al2O3(10) and lattice-doped NFM#Ti(35)#Al(10) cathodes (the number in parentheses responds to the cycles for ALD deposition) could maintain 319 and 358 cycles, respectively, more than that of the unmodified NFM cathode (250 cycles). Moreover, two modified cathodes also underwent their thermal runaway temperatures to 285.9 and 289.5 ℃ on the fully-charged condition respectively, corresponding to the increment of 6.1 and 9.7 ℃ compared to the NFM via differential scanning calorimetric (DSC) measurements. In-situ differential electrochemical mass spectrometry (DEMS) was further employed to analyze gas components and corresponding contents in the first two cycles of three different cathodes. As a result, the surface coating benefits from restricting the generation of major H2 components by effectively suppressing the protonation of the electrolyte solvents.By contrast, the lattice doping works for impeding the follow-up reactions of decomposed products from the initial decomposition of electrolytes.
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