A Membrane-Free Rechargeable Seawater Battery Unlocked by Lattice Engineering

Wei Wen; Chao Geng; Xinran Li; Hongpeng Li; Jin-Ming Wu; Hisayoshi Kobayashi; Tulai Sun; Zhenyu Zhang; Dongliang Chao

doi:10.1002/adma.202312343

A Membrane-Free Rechargeable Seawater Battery Unlocked by Lattice Engineering

Adv Mater. 2024 May 1:e2312343. doi: 10.1002/adma.202312343. Online ahead of print.

Authors

Wei Wen¹, Chao Geng¹, Xinran Li², Hongpeng Li², Jin-Ming Wu³, Hisayoshi Kobayashi⁴, Tulai Sun⁵, Zhenyu Zhang⁶, Dongliang Chao²

Affiliations

¹ School of Mechanical and Electrical Engineering, Collaborative Innovation Center of Ecological Civilization, Hainan University, Haikou, 570228, China.
² Laboratory of Advanced Materials, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, School of Chemistry and Materials, Fudan University, Shanghai, 200433, China.
³ State Key Laboratory of Silicon and Advanced Semiconductor Materials, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
⁴ Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Kyoto, 606-8585, Japan.
⁵ Center for Electron Microscopy, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology and College of Chemical Engineering, Zhejiang University of Technology, Hangzhou, 310014, China.
⁶ Key Laboratory for Precision and Non-Traditional Machining Technology of Ministry of Education, Dalian University of Technology, Dalian, 116024, China.

PMID: 38691579
DOI: 10.1002/adma.202312343

Abstract

Seawater batteries that directly utilize natural seawater as electrolytes are ideal sustainable aqueous devices with high safety, exceedingly low cost, and environmental friendliness. However, the present seawater batteries are either primary batteries or rechargeable half-seawater/half-nonaqueous batteries because of the lack of suitable anode working in seawater. Here, a unique lattice engineering to unlock the electrochemically inert anatase TiO₂ anode to be highly active for the reversible uptake of multiple cations (Na⁺, Mg²⁺, and Ca²⁺) in aqueous electrolytes is demonstrated. Density functional theory calculations further reveal the origin of the unprecedented charge storage behaviors, which can be attributed to the significant reduction of the cations diffusion barrier within the lattice, i.e., from 1.5 to 0.4 eV. As a result, the capacities of anatase TiO₂ with 2.4% lattice expansion are ≈100 times higher than the routine one in natural seawater, and ≈200 times higher in aqueous Na⁺ electrolyte. The finding will significantly advance aqueous seawater energy storage devices closer to practical applications.

Keywords: aqueous Na‐ion batteries; aqueous batteries; lattice expansion; seawater batteries; titanium dioxide.

Abstract

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