Boron Substituted Na ₃ V ₂ (P _{1 -x} B _x O ₄ ) ₃ Cathode Materials with Enhanced Performance for Sodium-Ion Batteries

Journal Article · Tue Aug 02 00:00:00 EDT 2016 · Advanced Science

DOI:https://doi.org/10.1002/advs.201600112· OSTI ID:1337183

Hu, Pu ^[1]; Wang, Xiaofang ^[2]; Wang, Tianshi ^[3]; Chen, Lanli ^[2]; Ma, Jun ^[3]; Kong, Qingyu ^[4]; Shi, Siqi ^[2]; Cui, Guanglei ^[3]

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1. Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 P. R. China; University of Chinese Academy of Sciences, Beijing 100049 P. R. China
2. School of Materials Science and Engineering, Shanghai University, Shanghai 200444 P. R. China; Materials Genome Institute, Shanghai University, Shanghai 200444 P. R. China
3. Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101 P. R. China
4. Société civile Synchrotron SOLEIL, L'Orme des Merisiers, Saint-Aubin - BP 48 91192 Gif-sur-Yvette CEDEX France

The development of excellent performance of Na-ion batteries remains great challenge owing to the poor stability and sluggish kinetics of cathode materials. Herein, B substituted Na₃V₂P_3–xB_xO₁₂ (0 ≤ x ≤ 1) as stable cathode materials for Na-ion battery is presented. A combined experimental and theoretical investigations on Na₃V₂P_3–xB_xO₁₂ (0 ≤ x ≤ 1) are undertaken to reveal the evolution of crystal and electronic structures and Na storage properties associated with various concentration of B. X-ray diffraction results indicate that the crystal structure of Na₃V₂P_3–xB_xO₁₂ (0 ≤ x ≤ 1/3) consisted of rhombohedral Na₃V₂(PO₄)₃ with tiny shrinkage of crystal lattice. X-ray absorption spectra and the calculated crystal structures all suggest that the detailed local structural distortion of substituted materials originates from the slight reduction of V–O distances. Na₃V₂P_3-1/6B_1/6O₁₂ significantly enhances the structural stability and electrochemical performance, giving remarkable enhanced capacity of 100 and 70 mAh g^-1 when the C-rate increases to 5 C and 10 C. Spin-polarized density functional theory (DFT) calculation reveals that, as compared with the pristine Na₃V₂(PO₄)₃, the superior electrochemical performance of the substituted materials can be attributed to the emergence of new boundary states near the band gap, lower Na⁺ diffusion energy barriers, and higher structure stability.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: USDOE
• OSTI ID: 1337183
• Journal Information: Advanced Science, Vol. 3, Issue 12; ISSN 2198-3844
• Publisher: Wiley
• Country of Publication: United States
• Language: ENGLISH

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36 MATERIALS SCIENCE