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·2026
Structurally Coordinated Water Enhances Structural Stability of Tunnel‐Type Co(VO 3 ) 2 ·2H 2 O Cathodes for Aqueous Zinc‐Ion Batteries
Hyeonjun Lee, Sangki Lee, Jangwook Pyun, Seunghyeop Baek, Doron Aurbach, Munseok S. Chae
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초록

Tunnel-type cobalt vanadate dihydrate (Co(VO<sub>3</sub>)<sub>2</sub>·2H<sub>2</sub>O, CoVO) is first demonstrated as a robust cathode for aqueous Zn-ion batteries. The orthorhombic framework, built from CoO<sub>6</sub> octahedra and VO<sub>4</sub> tetrahedra, incorporates two structural water molecules directly coordinated to Co<sup>2+</sup>. These structural waters serve critical functions: 1) forming hydrogen-bond networks that buffer local strain, 2) shielding electrostatic repulsion between Zn<sup>2+</sup> and the polyanionic framework, and 3) creating secondary diffusion channels that accelerate H<sup>+</sup>/Zn<sup>2+</sup> transport. Owing to this cooperative effect, CoVO delivers 83.6 mAh/g at 0.5C and retains 90.6% capacity after 1000 cycles at 3C. Ex situ XRD and Rietveld refinements confirm a topotactic, zero-strain intercalation mechanism (ΔV = 0.17%) without bulk decomposition, while bond valence sum analysis reveals dual-ion pathways with low migration barriers. The synergy between tunnel topology and structural water coordination underpins the exceptional rate capability, minimal impedance growth, and long-term stability, establishing a general design strategy for advanced multivalent-ion battery cathodes.

키워드
CathodeStructural stabilityAqueous solutionRietveld refinementOrthorhombic crystal systemIntercalation (chemistry)Octahedron
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2026

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