Unveiling a high capacity multi-redox (Nb5+/Nb4+/Nb3+) NASICON-Nb2(PO4)3 anode for Li- and Na-ion batteries

Patra, Biplab; Kumar, Keshav; Deb, Debolina; Ghosh, Subham; Gautam, Gopalakrishnan Sai; Senguttuvan, Premkumar

doi:10.1039/d2ta05971a

Unveiling a high capacity multi-redox (Nb⁵⁺/Nb⁴⁺/Nb³⁺) NASICON-Nb₂(PO₄)₃ anode for Li- and Na-ion batteries

Journal Article · Mon Feb 20 23:00:00 EST 2023 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d2ta05971a· OSTI ID:2423729

^[1]; ^[1]; Deb, Debolina ^[2]; Ghosh, Subham ^[1]; ^[2]; ^[1]

Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bengaluru (India)
Indian Institute of Science (IIS), Bengaluru (India)

Sodium superionic conductor (NASICON)-type materials are widely explored as Li- and Na-ion cathodes and solid-state electrolytes but are largely ignored as anodes due to their lower capacities and higher intercalation voltages, which reduce the overall energy densities of Li- and Na-ion batteries (LIBs and SIBs). Herein, we unveil high capacity multi-redox empty NASICON-Nb₂(PO₄)₃ as a potential anode material for LIBs and SIBs, which reversibly delivers 167 and 150 mA h g^-1 at the average voltages of 1.86 V vs. Li⁺/Li⁰ and 1.46 V vs. Na⁺/Na⁰, respectively. The Li and Na intercalation reactions proceed via multiple phase transitions, leading to short-range ordered Li₃Nb₂(PO₄)₃ and triclinic (P$$\overline{1}$$ with combining macron]) Na₃Nb₂(PO₄)₃, as revealed by in situ X-ray diffraction studies. Our density functional theory calculations are also in agreement with the in situ measurements in predicting a stable Na₃Nb₂(PO₄)₃ composition in the Na–Nb₂(PO₄)₃ pseudo-binary system. X-ray absorption spectroscopy confirms the participation of multi-redox Nb⁵⁺/Nb⁴⁺/Nb³⁺ couples. The Nb₂(PO₄)₃ anode delivers capacities greater than 124 and 106 mA h g^-1 at 1C rate in Li and Na cells, respectively. In conclusion, pairing Nb₂(PO₄)₃ with suitable cathodes and electrolytes can lead to high energy density batteries.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Government of India

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2423729

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 15 Vol. 11; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
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Lithium- and sodium-ion batteries
Materials Science
NASICON
Nb2(PO4)3
multi-redox anode

Unveiling a high capacity multi-redox (Nb5+/Nb4+/Nb3+) NASICON-Nb2(PO4)3 anode for Li- and Na-ion batteries

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Unveiling a high capacity multi-redox (Nb⁵⁺/Nb⁴⁺/Nb³⁺) NASICON-Nb₂(PO₄)₃ anode for Li- and Na-ion batteries