Chinese Journal of Rare Metals

2026, v.50;No.366(09) 1544-1561

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Research Progress on Aqueous Zinc-Ion Battery Cathode Materials Doped with Rare-Earth and High-Value Transition Metals

Yin Chengjie;Jia Rui;Hu Jinsong;

Abstract：

Aqueous zinc-ion batteries(AZIBs) are promising for safe and cost-effective energy storage, yet their vanadium-and manganese-based cathodes suffer from low conductivity, sluggish Zn~(2+) diffusion, structural degradation, and active-material dissolution. Ion doping has been extensively explored to address these issues, but a systematic comparison between rare-earth elements and high-value transition metals regarding their distinct regulatory effects remains lacking. This review provided a comparative analysis of rare-earth(La, Ce, Y, Pr, Eu) and high-value transition-metal(Ag, Ru, Mo) doped V-based and Mn-based cathodes, focusing on how each dopant category influences interlayer spacing, defect chemistry, bond strength, and electrochemical kinetics, and identified remaining bottlenecks for rational cathode design. The review first summarized the charge-storage mechanisms of V-and Mn-based cathodes using ex-situ X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and electrochemical impedance spectroscopy. Vanadium oxides involved Zn~(2+) intercalation, H~+/Zn~(2+) co-intercalation with structural water, and irreversible phase transformation. Manganese oxides exhibited H~+ insertion, Zn~(2+) insertion, and dissolution-deposition of Mn~(2+) intermediates, with the specific route depending on the polymorph and electrolyte pH. Based on these mechanistic insights, the review evaluated doping strategies for each category. Rare-earth doping was examined through density functional theory calculations of band structures and lattice parameters, combined with electrochemical testing of interlayer expansion, oxygen-vacancy formation, and cycling stability. High-value transition-metal doping was assessed via theoretical models including the energy difference between metal d-band and O 2p-band centers, in-situ spectroscopic characterization, galvanostatic intermittent titration technique for ion diffusion coefficients, and crystal orbital Hamilton population analysis for bond-strength variations. For rare-earth doping, La~(3+) intercalation into V_2O_5 expanded the lattice parameters and reduces the band gap, leading to improved discharge capacity and cycling stability. Ce~(3+) doping in MnO_2 induced a phase transition from β to α with larger tunnels, enhancing ion transport. Y~(3+) pre-intercalation narrowed the band gap and substantially improved long-term cycling retention. Eu~(3+) doping reduced charge-transfer resistance and stabilizes cycling performance. Pr_6O_(11)-Mn_2O_3 heterostructures, constructed via cation exchange, showed enhanced Mn-O interactions due to 4f orbital modulation, as confirmed by density functional theory(DFT) analyses. Overall, rare-earth elements functioned through pillar effects, oxygen-vacancy introduction, and band-gap modulation. For high-value transition metals, Ag~+ pre-intercalation in V_2O_5 generated in-situ Ag nanoparticles during discharge, enhancing electronic conduction and promoting reversible basic zinc salt formation for additional surface storage. In Ag_2Mn_8O_(16), an anodically formed AgCl interfacial layer suppressed Mn dissolution and stabilized cycling. Ru-based heterostructures with V-O-Ru bonds exhibited significantly increased ionic diffusion coefficients and exceptional rate capability; Ru doping in MnO_2 broadened the O p-band and suppresses Jahn-Teller distortion. Mo doping, guided by the Δd-p theoretical model, stabilized the host structure; oxygen-vacancy engineering further enhances capacity and retention. Zn/Mo co-intercalation delivered high capacity with stable long-term cycling. In MnO_2, Mo~(6+) strengthened Mn-O bonds, inhibited Mn~(3+) disproportionation, and reduced dissolution. Mo-doped γ-MnO_2 with increased specific surface area showed enhanced performance, and NH~(4+) co-insertion constructed a hydrogen-bond network that further stabilized the lattice. Rare-earth doping primarily stabilized the host structure via pillar effects, introduced oxygen vacancies, and narrowed the band gap through 4f orbital perturbation, enhancing Zn~(2+) diffusion kinetics and cycle life. High-value transition metals mainly improved intrinsic conductivity, promoted synergistic H~+/Zn~(2+) co-storage, and reinforced M-O bonding to suppress dissolution. Despite these advances, challenges remained regarding the high cost and scarcity of these elements, the lack of scalable synthesis routes, and the unclear environmental impact of potential ion leaching. Most studies focused on single-element doping, whereas co-doping and multi-element synergistic effects were rarely explored. Future work should develop mild and scalable doping techniques, integrate in-situ characterizations with computational approaches to establish predictive doping models, and adopt system-level optimization coupling cathode doping with anode protection and electrolyte engineering. A balanced assessment of performance, cost, scalability, and environmental sustainability was essential for practical translation. Additionally, the mechanistic understanding of dopant-host-electrolyte interactions remained incomplete, and the absence of standardized evaluation protocoled hampers cross-study comparison.

Key Words： aqueous zinc-ion batteries(AZIBs);cathode materials;rare earth metals;high-value transition metals

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Foundation: 安徽高校自然科学研究项目（2024AH050395）资助

Authors: Yin Chengjie;Jia Rui;Hu Jinsong;

DOI: 10.13373/j.cnki.cjrm.XY25070004

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