NASICON Na3V2(PO4)3 Enables Quasi-Two-Stage Na+ and Zn2+ Intercalation for Multivalent Zinc Batteries
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- 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+).
- Research Organization:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; US Department of the Navy, Office of Naval Research (ONR)
- Grant/Contract Number:
- AC02-76SF00515; N000141712244; AC36-08GO28308
- OSTI ID:
- 1633610
- Alternate ID(s):
- OSTI ID: 1660079
- Report Number(s):
- NREL/JA-5K00-77329; TRN: US2201214
- Journal Information:
- Chemistry of Materials, Vol. 32, Issue 7; ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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