Cross‐Doped Mn/Mo Oxides with Core‐Shell Structures Designed by a Self‐Template Strategy for Durable Aqueous Zinc‐Ion Batteries

Abstract

Manganese oxide as the star cathode material of aqueous zinc ion batteries is vigorously developed because of its environmental protection, outstanding theoretical capacity, and high voltage. However, severe Jahn–Teller distortion of trivalent Mn has detrimental effect on cyclic stability. Herein, 1D core‐shell bimetal oxide with cross‐doping of heteroatom is successfully designed by self‐template method via one‐step hydrothermal reaction. Specifically, the thick shell of Mo‐doped α‐MnO2 with increased nanopores, expanded lattice spacing, and high oxidation state not only contributes high capacity but also suppresses the lattice distortion due to the doping of high‐valent Mo6+; While the thin core of Mn‐doped MoO3 nanobelt supplies a shaped template, important Mo source, and improved conductive path. Therefore, this composite exhibits a superior capacity of 366.2 mAh g−1 at 0.2 A g−1 and 100% capacity retention after 100 cycles, which effectively increases to 4.1 times from 1.5 times of pure α‐MnO2 based battery. Besides promoting the electrochemical performance in coin‐cell batteries, composite materials also balance the electrochemical and mechanical performances in flexible micro‐batteries with area energy density of 261.2 µWh cm−2. Therefore, this synergetic self‐template and cross‐doping strategy can extend to the material design of other high‐performance metal oxides for energy storage application.

High-rate and long-life flexible aqueous rechargeable zinc-ion battery enabled by hierarchical core–shell heterostructures

“…The bimetallic oxides are composed of Mo-doped α-MnO 2 nanoparticles as the shell and Mn-doped MoO 3 nanobelts as the core, exhibiting the advantages of large specific surface area, resistance to mechanical deformation, and enlarged diffusion channels. 39…”

Development of plasma technology for the preparation and modification of energy storage materials

“…Extensive research has demonstrated the enhanced intrinsic properties of energy storage materials through the introduction of heteroatom doping or functional group modification. This is commonly achieved through various methodologies, including high temperature sintering, 1,2 co-precipitation, 3,4 hydrothermal reactions, 5–7 vapor deposition (CVD/PVD), 8,9 chemical reactions, and other similar approaches. These techniques lead to improvements in specific capacity, initial efficiency, and rate capability of energy storage materials by inducing the formation of defects, vacancies, active sites, 10 etc.…”

Phase-Modified Strongly Coupled δ/ε-MnO2 Homojunction Cathode for Kinetics-Enhanced Zinc-Ion Batteries

“…This phenomenon is particularly common in aqueous zinc-ion batteries (AZIBs) with MnO 2 as the cathode material. To solve these problems, a series of effective strategies have been developed, such as heteroatom doping, defect engineering, bond/interface engineering, nanostructure design, electrolyte modification, and surface coating. − …”