4.6 Article

Stabilized Phase Transition Process of Layered NaxCoO2 via Ca-Substitution

期刊

出版社

ELECTROCHEMICAL SOC INC
DOI: 10.1149/1945-7111/abd451

关键词

sodium-ion batteries; layered cathodes; phase transition; degradation; cycling performance

资金

  1. Element Strategy Initiative of MEXT [JPMXP0112101003]
  2. KAKENHI of MEXT [19H05813]
  3. KAKENHI of JSPS [18K19131]
  4. Grants-in-Aid for Scientific Research [19H05813, 18K19131] Funding Source: KAKEN

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The study found that Ca substitution in NaxCoO2 affects its capacity fading during charge and discharge cycles, mainly due to the migration of Co3+/4+ ions. Although Ca substitution does not completely prevent phase transitions, it does improve capacity retention.
We investigated the suppressed capacity fading of a Ca-substituted P3-type NaxCoO2 during the charge/discharge process. The Ca-substituted NaxCoO2 shows similar phase transition behavior to the Ca free one, with an expanded P ' 3 phase region. The capacity fading of the NaxCoO2 is highly correlated with the phase transition at 4.0 V of P ' 3-O3 ' phase transition and at 2.7 V of O ' 3-P ' 3 phase transition. The amount of Co3O4 observed in the cycled electrodes corresponds to the capacity loss during the cycling test. Thus, the migration of the Co3+/4+ ions during the phase transition process causes the capacity fading. The decomposition of the electrolyte solution also accelerates the migration of the Co3+/4+ ions. Though the Ca-substitution does not prevent the phase transition, the Ca-substituted NaxCoO2 shows improved capacity retention.

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