Journal
JOURNAL OF MATERIALS CHEMISTRY A
Volume 9, Issue 17, Pages 10803-10811Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1ta01433a
Keywords
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Funding
- National Natural Science Foundation of China [11975238, 11575192, 21776275]
- Chinese Academy of Sciences [211211KYSB20170060, 211211KYSB20180020, ZDKYYQ20170001, XDB28000000]
- Natural Science Foundation of Beijing [2182082]
- Fundamental Research Funds for the Central Universities
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In this study, a controlled F-/Ca2+ dual-doping strategy was proposed to mitigate the P2-O2 phase transition, significantly improving the structural stability and cycling performance. The doping of Ca2+ and F- facilitated electronic and ionic conductivity, enhancing the high-rate capability.
P2-type Na2/3Ni1/3Mn2/3O2 is one of the most promising cathode candidates for sodium-ion batteries due to its high specific capacity and high working voltage. However, a detrimental P2-O2 phase transition usually occurs at a high voltage (>4.2 V) leading to poor cycle stability. Herein, we propose to mitigate this critical issue through a controlled F-/Ca2+ dual-doping strategy with CaF2 as a dopant. The divalent Ca2+ ion doped in the Na layer stabilizes the layered structure at a high voltage when excessive Na+ is extracted. The more electronegative F- ion forms a stronger transition metal (TM)-F bond and reduces the electrostatic repulsion between the oxygen layers impeding the gliding of TMO2 layers. The Ca2+/F- co-doping successfully suppresses the unfavorable P2-O2 phase transition, and significantly improves the structural stability and cycling performance (27.1% vs. 87.2% after 500 cycles at 1C). Furthermore, density functional theory calculations combined with experimental tests reveal that the incorporation of Ca2+ and F- in Na sites and O sites facilitates the electronic and ionic conductivity owing to Na+/vacancy disordering, which enhances the high-rate capability. This study provides some insights into the design of long-life and high-rate cathode materials for sodium-ion batteries.
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