Surface-redox sodium-ion storage in anatase titanium oxide

Qiulong Wei (), Xiaoqing Chang, Danielle Butts, Ryan DeBlock, Kun Lan, Junbin Li, Dongliang Chao, Dong-Liang Peng and Bruce Dunn ()
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Qiulong Wei: Xiamen University
Xiaoqing Chang: Xiamen University
Danielle Butts: University of California Los Angeles
Ryan DeBlock: University of California Los Angeles
Kun Lan: Fudan University
Junbin Li: Xiamen University
Dongliang Chao: Fudan University
Dong-Liang Peng: Xiamen University
Bruce Dunn: University of California Los Angeles

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Sodium-ion storage technologies are promising candidates for large-scale grid systems due to the abundance and low cost of sodium. However, compared to well-understood lithium-ion storage mechanisms, sodium-ion storage remains relatively unexplored. Herein, we systematically determine the sodium-ion storage properties of anatase titanium dioxide (TiO2(A)). During the initial sodiation process, a thin surface layer (~3 to 5 nm) of crystalline TiO2(A) becomes amorphous but still undergoes Ti4+/Ti3+ redox reactions. A model explaining the role of the amorphous layer and the dependence of the specific capacity on the size of TiO2(A) nanoparticles is proposed. Amorphous nanoparticles of ~10 nm seem to be optimum in terms of achieving high specific capacity, on the order of 200 mAh g−1, at high charge/discharge rates. Kinetic studies of TiO2(A) nanoparticles indicate that sodium-ion storage is due to a surface-redox mechanism that is not dependent on nanoparticle size in contrast to the lithiation of TiO2(A) which is a diffusion-limited intercalation process. The surface-redox properties of TiO2(A) result in excellent rate capability, cycling stability and low overpotentials. Moreover, tailoring the surface-redox mechanism enables thick electrodes of TiO2(A) to retain high rate properties, and represents a promising direction for high-power sodium-ion storage.

Date: 2023
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DOI: 10.1038/s41467-022-35617-3

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