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Highly porous, low band-gap NixMn3-xO4 (0.55 ≤ x ≤ 1.2) spinel nanoparticles with in situ coated carbon as advanced cathode materials for zinc-ion batteries

Journal Article


Abstract


  • 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.

Authors


  •   Long, Jun (external author)
  •   Gu, Jinxing (external author)
  •   Yang, Zhanhong (external author)
  •   Mao, Jianfeng
  •   Hao, Junnan (external author)
  •   Chen, Zhongfang (external author)
  •   Guo, Zaiping

Publication Date


  • 2019

Citation


  • Long, J., Gu, J., Yang, Z., Mao, J., Hao, J., Chen, Z. & Guo, Z. (2019). Highly porous, low band-gap NixMn3-xO4 (0.55 ≤ x ≤ 1.2) spinel nanoparticles with in situ coated carbon as advanced cathode materials for zinc-ion batteries. Journal of Materials Chemistry A, 7 (30), 17854-17866.

Scopus Eid


  • 2-s2.0-85070079841

Number Of Pages


  • 12

Start Page


  • 17854

End Page


  • 17866

Volume


  • 7

Issue


  • 30

Place Of Publication


  • United Kingdom

Abstract


  • 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.

Authors


  •   Long, Jun (external author)
  •   Gu, Jinxing (external author)
  •   Yang, Zhanhong (external author)
  •   Mao, Jianfeng
  •   Hao, Junnan (external author)
  •   Chen, Zhongfang (external author)
  •   Guo, Zaiping

Publication Date


  • 2019

Citation


  • Long, J., Gu, J., Yang, Z., Mao, J., Hao, J., Chen, Z. & Guo, Z. (2019). Highly porous, low band-gap NixMn3-xO4 (0.55 ≤ x ≤ 1.2) spinel nanoparticles with in situ coated carbon as advanced cathode materials for zinc-ion batteries. Journal of Materials Chemistry A, 7 (30), 17854-17866.

Scopus Eid


  • 2-s2.0-85070079841

Number Of Pages


  • 12

Start Page


  • 17854

End Page


  • 17866

Volume


  • 7

Issue


  • 30

Place Of Publication


  • United Kingdom