NASICON Na3V2(PO4)3 Enables Quasi-Two-Stage Na+ and Zn2+ Intercalation for Multivalent Zinc Batteries

Ko, Jesse S.; Paul, Partha P.; Wan, Gang; Seitzman, Natalie; DeBlock, Ryan Henry; Dunn, Bruce S.; Toney, Michael F.; Nelson Weker, Johanna

doi:10.1021/acs.chemmater.0c00004

NASICON Na₃V₂(PO₄)₃ Enables Quasi-Two-Stage Na⁺ and Zn²⁺ Intercalation for Multivalent Zinc Batteries

Journal Article · Wed Mar 11 00:00:00 EDT 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c00004· OSTI ID:1633610

^[1]; Paul, Partha P. ^[1]; Wan, Gang ^[1]; Seitzman, Natalie ^[2]; ^[3]; ^[3]; ^[1]; ^[1]

SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Univ. of California, Los Angeles, CA (United States). Dept. of Materials Science and Engineering

Identifying positive electrode materials capable of reversible multivalent electrochemistry in electrolytes containing divalent ions such as Mg²⁺, Ca²⁺, and Zn²⁺ at high operating potentials remains an ongoing challenge in “beyond lithium-ion” research. In this paper, we explore the Zn²⁺ charge-storage mechanism of a vanadium-based Na⁺ superionic conductor (NASICON), Na₃V₂(PO₄)₃. By using X-ray synchrotron techniques to unravel potential-dependent structure–property relationships, we ascribe the reversible electrochemical behavior of Na₃V₂(PO₄)₃ to a quasi-two-stage intercalation process that involves both Na+ and Zn²⁺. Initial charging of Na₃V₂(PO₄)₃ leads to a Na⁺-extracted phase corresponding to Na₃V₂(PO₄)₃, whereas subsequent discharge results predominantly in Na⁺ intercalation followed by Zn²⁺ intercalation. Operando X-ray diffraction of Na₃V₂(PO₄)₃ was used to study the phase changes associated with the first charge/discharge process, and ex situ measurements were used to precisely link the changes in the crystal structure to a quasi-two-stage intercalation of Na⁺ and Zn²⁺. The corresponding changes in the V-oxidation state, V-O coordination, and the presence of Zn²⁺ were confirmed by X-ray absorption spectroscopy. The results of this work present a comprehensive understanding of the charge-storage properties for a well-established NASICON structure that confers both the high capacity (~100 mA h g^-1) and high potential (1.35 and 1.1 V vs Zn/Zn²⁺).

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: US Department of the Navy, Office of Naval Research (ONR); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; AC36-08GO28308

OSTI ID:: 1633610

Alternate ID(s):: OSTI ID: 1660079

Report Number(s):: NREL/JA-5K00-77329

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 7 Vol. 32; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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NASICON Na3V2(PO4)3 Enables Quasi-Two-Stage Na+ and Zn2+ Intercalation for Multivalent Zinc Batteries

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NASICON Na₃V₂(PO₄)₃ Enables Quasi-Two-Stage Na⁺ and Zn²⁺ Intercalation for Multivalent Zinc Batteries