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Gradient fluorination engineering through interdiffusion reaction for high-voltage LiCoO2
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DOI：10.1016/j.ensm.2024.103446.png)
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The advancement of high charging cut-off voltage stands as a crucial avenue to enhance the energy density of LiCoO2 (LCO). However, LCO faces severe interface and bulk phase issues at high voltage (>= 4.6 V), resulting in poor cycling stability. In this study, we reconstruct the surface structure of LCO based on the interdiffusion reaction between LCO and MgF2 in a high-temperature sintering process. Specifically, this interdiffusion reaction yields an ultra-thin LiF coating layer, artificially reinforcing the chemical structure of the cathode-electrolyte interphase (CEI) during cycling. This LiF-rich CEI not only effectively protects the surface structure of LCO, but also facilitates the lithium-ion diffusion. Furthermore, the diffusion of F and Mg into the LCO lattice significantly strengthens the structure, which inhibits unfavorable phase transitions from the O3 phase to the H1-3 phase at high voltage. Consequently, such modified LCO with concurrently enhanced interface and bulk structure exhibits outstanding long-term cycling performance within 3.0-4.6 V at 1 C, achieving a capacity retention of 84.9 % after 1000 cycles. Meanwhile, it also demonstrates excellent high-temperature performance, with a capacity retention of 85.0 % after 200 cycles under 45 degrees C.
Keyword:
Interdiffusion reaction
Phase transition
Interface stabilization
Cycle stability
High-voltage LiCoO2
期刊
IF:
20.2
论文数:
5.7K
被引数:
6.3W
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