Operando X-ray Studies of Ni-Containing Heteropolyvanadate Electrode for High-Energy Lithium-Ion Storage Applications

Tsung-Yi Chen; Ho Viet Thang; Tien-Yu Yi; Shao-Chu Huang; Chia-Ching Lin; Yu-Ming Chang; Pei-Lin Chen; Ming-Hsien Lin; Jyh-Fu Lee; Hsin-Yi Tiffany Chen; Chi-Chang Hu; Han-Yi Chen

doi:10.1021/acsami.2c16777

Operando X-ray Studies of Ni-Containing Heteropolyvanadate Electrode for High-Energy Lithium-Ion Storage Applications

ACS Appl Mater Interfaces. 2022 Nov 23;14(46):52035-52045. doi: 10.1021/acsami.2c16777. Epub 2022 Nov 8.

Authors

Tsung-Yi Chen^{1

2}, Ho Viet Thang³, Tien-Yu Yi⁴, Shao-Chu Huang¹, Chia-Ching Lin¹, Yu-Ming Chang¹, Pei-Lin Chen⁵, Ming-Hsien Lin⁶, Jyh-Fu Lee⁷, Hsin-Yi Tiffany Chen^{8

9}, Chi-Chang Hu⁴, Han-Yi Chen^{1

2}

Affiliations

¹ Department of Materials Science and Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu300044, Taiwan.
² High Entropy Materials Center, 101, Sec. 2, Kuang-Fu Road, Hsinchu300044, Taiwan.
³ The University of Da-Nang, University of Science and Technology, 54 Nguyen Luong Bang, Da Nang550000, Vietnam.
⁴ Department of Chemical Engineering, National Tsing Hua University, Hsinchu300044, Taiwan.
⁵ Instrumentation Center, National Tsing Hua University, Hsinchu300044, Taiwan.
⁶ Department of Chemical and Materials Engineering, Chung Cheng Institute of Technology, National Defense University, Tashi, Taoyuan33551, Taiwan.
⁷ National Synchrotron Radiation Research Center, Hsinchu30076, Taiwan.
⁸ Department of Engineering and System Science, National Tsing Hua University, Hsinchu300044, Taiwan.
⁹ College of Semiconductor Research, National Tsing Hua University, Hsinchu300044, Taiwan.

PMID: 36346965
DOI: 10.1021/acsami.2c16777

Abstract

Ni-containing heteropolyvanadate, Na₆[NiV₁₄O₄₀], was synthesized for the first time to be applied in high-energy lithium storage applications as a negative electrode material. Na₆[NiV₁₄O₄₀] can be prepared via a facile solution process that is suitable for low-cost mass production. The as-prepared electrode provided a high capacity of approximately 700 mAh g^-1 without degradation for 400 cycles, indicating excellent cycling stability. The mechanism of charge storage was investigated using operando X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), transition X-ray microscopy (TXM), and density functional theory (DFT) calculations. The results showed that V⁵⁺ was reduced to V²⁺ during lithiation, indicating that Na₆[NiV₁₄O₄₀] is an insertion-type material. In addition, Na₆[NiV₁₄O₄₀] maintained its amorphous structure with negligible volume expansion/contraction during cycling. Employed as the negative electrode in a lithium-ion battery (LIB), the Na₆[NiV₁₄O₄₀]//LiFePO₄ full cell had a high energy density of 300 W h kg^-1. When applied in a lithium-ion capacitor, the Na₆[NiV₁₄O₄₀]//expanded mesocarbon microbead full cell displayed energy densities of 218.5 and 47.9 W h kg^-1 at power densities of 175.7 and 7774.2 W kg^-1, respectively. These findings reveal that the negative electrode material Na₆[NiV₁₄O₄₀] is a promising candidate for Li-ion storage applications.

Keywords: X-ray absorption spectroscopy; anode; heteropolyvanadate; lithium-ion storage; polyoxometalate.