Zinc‐Doping Strategy on P2‐Type Mn‐Based Layered Oxide Cathode for High‐Performance Potassium‐ion Batteries

Abstract

Mn-based layered oxide is extensively investigated as a promising cathode material for potassium-ion batteries due to its high theoretical capacity and natural abundance of manganese. However, the Jahn-Teller distortion caused by high-spin Mn³⁺ (t_2g ³ e_g ¹ ) destabilizes the host structure and reduces the cycling stability. Here, K_0.02 Na_0.55 Mn_0.70 Ni_0.25 Zn_0.05 O₂ (denoted as KNMNO-Z) is reported to inhibit the Jahn-Teller effect and reduce the irreversible phase transition. Through the implementation of a Zn-doping strategy, higher Mn valence is achieved in the KNMNO-Z electrode, resulting in a reduction of Mn³⁺ amount and subsequently leading to an improvement in cyclic stability. Specifically, after 1000 cycles, a high retention rate of 97% is observed. Density functional theory calculations reveals that low-valence Zn²⁺ ions substituting the transition metal position of Mn regulated the electronic structure around the MnO bonding, thereby alleviating the anisotropic coupling between oxidized O^2- and Mn⁴⁺ and improving the structural stability. K_0.02 Na_0.55 Mn_0.70 Ni_0.25 Zn_0.05 O₂ provided an initial discharge capacity of 57 mAh g^-1 at 100 mA g^-1 and a decay rate of only 0.003% per cycle, indicating that the Zn-doped strategy is effective for developing high-performance Mn-based layered oxide cathode materials in PIBs.