期刊
JOURNAL OF MATERIALS CHEMISTRY A
卷 7, 期 30, 页码 17854-17866出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9ta05101e
关键词
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资金
- National Natural Science Foundation of China [21371180]
- Australian Research Council (ARC) [FT150100109, DP170102406]
- National Science Foundation-Centers of Research Excellence in Science and Technology (NSF-CREST Center) for Innovation, Research and Education in Environmental Nanotechnology (CIRE2N) [HRD-1736093]
- China Scholarship Council (CSC) [201706370175]
Aqueous zinc ion batteries (ZIBs) are emerging as a highly promising alternative technology for grid-scale applications where high safety, environmental-friendliness, and high specific capacities are needed. It remains a significant challenge, however, to develop a cathode with a high rate capability and long-term cycling stability. Here, we demonstrate diffusion-controlled behavior in the intercalation of zinc ions into highly porous, Mn4+-rich, and low-band-gap NixMn3-xO4 nano-particles with a carbon matrix formed in situ (with the composite denoted as NixMn3-xO4@C, x = 1), which exhibits superior rate capability (139.7 and 98.5 mA h g(-1) at 50 and 1200 mA g(-1), respectively) and outstanding cycling stability (128.8 mA h g(-1) remaining at 400 mA g(-1) after 850 cycles). Based on the obtained experimental results and density functional theory (DFT) calculations, cation-site Ni substitution combined with a sufficient doping concentration can decrease the band gap and effectively improve the electronic conductivity in the crystal. Furthermore, the amorphous carbon shell and highly porous Mn4+-rich structure lead to fast electron transport and short Zn2+ diffusion paths in a mild aqueous electrolyte. This study provides an example of a technique to optimize cathode materials for high-performance rechargeable ZIBs and design advanced intercalation-type materials for other energy storage devices.
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