Challenges and Perspectives for Doping Strategy for Manganese-Based Zinc-ion Battery Cathode

Abstract

As one of the most appealing options for large-scale energy storage systems, the commercialization of aqueous zinc-ion batteries (AZIBs) has received considerable attention due to their cost effectiveness and inherent safety. A potential cathode material for the commercialization of AZIBs is the manganese-based cathode, but it suffers from poor cycle stability, owing to the Jahn–Teller effect, which leads to the dissolution of Mn in the electrolyte, as well as low electron/ion conductivity. In order to solve these problems, various strategies have been adopted to improve the stability of manganese-based cathode materials. Among those, the doping strategy has become popular, where the dopant is inserted into the intrinsic crystal structures of electrode materials, which would stabilize them and tune the electronic state of the redox center to realize high ion/electron transport. Herein, we summarize the ion doping strategy from the following aspects: (1) synthesis strategy of doped manganese-based oxides; (2) valence-dependent dopant ions in manganese-based oxides; (3) optimization mechanism of ion doping in zinc-manganese battery. Lastly, an in-depth understanding and future perspectives of ion doping strategy in electrode materials are provided for the commercialization of manganese-based zinc-ion batteries.

Facile Construction of Zn‐Doped Mn3O4−MnO2 Vertical Nanosheets for Aqueous Zinc‐Ion Battery Cathodes

“…As shown in Figure 5d, the ZnMM‐NSs electrode shows improved cycling durability with considerable capacity retention (69.4 %) after 200 cycles as compared with that of up‐doped one. From the post SEM analysis shown in Figure S5, we can observe that some cracks and aggregations are occurred in cycled ZnMM‐NSs sample which is ascribed to the possibility of manganese dissolution [54] . However, the 3D porous character for the active material still remains after 200 charge/discharge cycles, ensuring the structural stability and resulting in improved cyclability for the prepared material.…”

Electrochemical Activation in Vanadium Oxide with Rich Oxygen Vacancies for High-Performance Aqueous Zinc-Ion Batteries

“…Until now, cathode materials for ZIBs are extensively investigated including vanadium-based materials, − manganese-based oxides, − Prussian blue analogs, − MoS 2 − materials, and other emerging materials. For Prussian blue analogs, the low specific capacity, crystal defects, and low conductivity restrict their development. , Manganese-based oxides are prone to generate disproportionation reactions and structural collapse during cycling, in spite of their abundant and safe nature, which significantly affects the electrochemical performance of AZIBs . MoS 2 materials have high specific capacity, but poor electrical conductivity and cycle stability AZIBs that still need to be improved.…”

Potassium-Ion-Doped Manganese Oxides and Kaolinite Electrolyte Additives for Aqueous Zinc-Ion Batteries

“…However, the MnO 2 cathode will undergo severe structural degradation during the cycle, resulting in a decrease in the cycle performance. Several optimization strategies, such as structural design, 31 cationic doping, 32 carbon coating, and electrolyte additive, 33 have been reported to enhance the electrochemical performance of manganese oxides. Cationic doping, as a common strategy for structural modification, has been proven to be effective in improving the electrochemical performance.…”