Orbital-engineered layered MnO₂ cathode enabled by Ca²⁺ interlayer coupling in rechargeable calcium battery

TY - JOUR

T1 - Orbital-engineered layered MnO2 cathode enabled by Ca2+ interlayer coupling in rechargeable calcium battery

AU - Han, Xiaomin

AU - Wang, Lihua

AU - Zhao, Ran

AU - Yu, Luyang

AU - Gou, Zhaolin

AU - Yang, Jingjing

AU - Hu, Zhifan

AU - Lv, Mengge

AU - Wu, Feng

AU - Bai, Ying

AU - Wu, Chuan

N1 - Publisher Copyright: © 2025 Science Press

PY - 2026/5

Y1 - 2026/5

N2 - Developing multivalent-ion storage systems demands cathode materials that combine high structural adaptability with favorable orbital interactions to host sluggish, highly charged carriers such as Ca2+. Herein, a multi-synergistic interlayer engineering strategy is proposed via Ca2+ interlayer coordination. The pre-coordination of Ca2+ ions establishes Mn–O–Ca bridges that not only expand the interlayer distance but also reshape the local orbital field of Mn, thereby stabilizing the high-valence Mn states and suppressing Jahn-Teller distortion. Defect-induced orbital reconfiguration simultaneously enhances electronic delocalization and interlayer polarity by creating localized charge imbalances at oxygen vacancies. As a result, efficient charge transfer and Ca2+ diffusion are promoted, and more surface-active sites are exposed. Electrochemical evaluations reveal that Ca-MnO2 exhibits significantly improved reversible capacity (∼100 mA h g−1 at 0.1 A g−1) and long-term cycling stability (1200 cycles at 1 A g−1), outperforming pristine δ-MnO2. Kinetic analysis through CV, GITT, and EIS demonstrates enhanced Ca2+ diffusion coefficients and reduced polarization in the pre-intercalated material. These results demonstrate an orbital-coupled interlayer engineering route toward high-performance Mn-based hosts for next-generation multivalent batteries.

AB - Developing multivalent-ion storage systems demands cathode materials that combine high structural adaptability with favorable orbital interactions to host sluggish, highly charged carriers such as Ca2+. Herein, a multi-synergistic interlayer engineering strategy is proposed via Ca2+ interlayer coordination. The pre-coordination of Ca2+ ions establishes Mn–O–Ca bridges that not only expand the interlayer distance but also reshape the local orbital field of Mn, thereby stabilizing the high-valence Mn states and suppressing Jahn-Teller distortion. Defect-induced orbital reconfiguration simultaneously enhances electronic delocalization and interlayer polarity by creating localized charge imbalances at oxygen vacancies. As a result, efficient charge transfer and Ca2+ diffusion are promoted, and more surface-active sites are exposed. Electrochemical evaluations reveal that Ca-MnO2 exhibits significantly improved reversible capacity (∼100 mA h g−1 at 0.1 A g−1) and long-term cycling stability (1200 cycles at 1 A g−1), outperforming pristine δ-MnO2. Kinetic analysis through CV, GITT, and EIS demonstrates enhanced Ca2+ diffusion coefficients and reduced polarization in the pre-intercalated material. These results demonstrate an orbital-coupled interlayer engineering route toward high-performance Mn-based hosts for next-generation multivalent batteries.

KW - Interlayer engineering

KW - Jahn-Teller effect suppression

KW - Manganese dioxide

KW - Oxygen vacancies

KW - Rechargeable calcium battery

UR - https://www.scopus.com/pages/publications/105027547728

U2 - 10.1016/j.jechem.2025.12.012

DO - 10.1016/j.jechem.2025.12.012

M3 - Article

AN - SCOPUS:105027547728

SN - 2095-4956

VL - 116

SP - 1

EP - 11

JO - Journal of Energy Chemistry

JF - Journal of Energy Chemistry

ER -