4.8 Article

Manganese buffer induced high-performance disordered MnVO cathodes in zinc batteries

期刊

ENERGY & ENVIRONMENTAL SCIENCE
卷 14, 期 7, 页码 3954-3964

出版社

ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ee00590a

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资金

  1. National Key R&D Program of China [2020YFA0405800, 2017YFA0303500]
  2. NSFC [U1932201, U2032113, 22075264]
  3. CAS Collaborative Innovation Program of Hefei Science Center [2019HSC-CIP002, 2020HSC-CIP002]
  4. CAS Interdisciplinary Innovation Team
  5. National Postdoctoral Program for Innovative Talents [BX20190315]
  6. Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Nankai University (111 Project) [B12015]

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This study demonstrates the buffer role of Mn in an aqueous Zn-ion battery cathode, which stabilizes the electrode structure and modulates the Fermi surface by migrating Mn ions, leading to improved battery performance and cycling stability.
Buffer reactions can prevent changes induced by external causes. Here, we demonstrate the significant buffer role of a very small amount of Mn in a self-optimized cathode for an aqueous Zn-ion battery. Our operando X-ray characterization studies reveal that the dissolution of most of the Mn in MnV2O4 during the first charging cycle induces atomic re-arrangement to form a disordered vanadium oxide phase with 0.88 at% Mn. Interestingly, the residual Mn ions exhibit voluntary migration between tetrahedral and octahedral sites during Zn2+ de/intercalation. This Mn migration not only stabilizes the main structure of the vanadium-based electrode, but also modulates the Fermi surface of V 3d against excessive drift. As result, the optimized cathode delivers an excellent capacity of 610.2 mA h g(-1) at 0.2 A g(-1) and long-term cycling stability over 4000 cycles. This buffer contribution via tunable metal ions exhibits high potential for applications in long-life metal-ion batteries and related fields.

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