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From Solid Electrolyte to Zinc Cathode: Vanadium Substitution in ZnPS₃

Martinolich, Andrew J. and Ware, Skyler D. and Lee, Brian C. and See, Kimberly A. (2021) From Solid Electrolyte to Zinc Cathode: Vanadium Substitution in ZnPS₃. Journal of Physics: Materials, 4 (2). Art. No. 024005. ISSN 2515-7639. https://resolver.caltech.edu/CaltechAUTHORS:20210301-154055511

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Abstract

Development of next generation batteries is predicated on the design and discovery of new, functional materials. Divalent cations are promising options that go beyond the canonical Li-based systems, but the development of new materials for divalent ion batteries is hindered due to difficulties in promoting divalent ion conduction. We have developed a family of cathode materials based on the divalent cation conductor ZnPS₃. Substitution of V for Zn in the lattice concomitant with vacancy introduction yields isostructural but redox-active materials that can reversibly store Zn²⁺ in the vacancies. A range of voltammetry and galvanostatic cycling experiments along with x-ray photoelectron spectroscopy support that redox is indeed centered on V and that capacity is dependent on the V content. The voltage of the materials is limited by the irreversible decomposition of the [P₂S₆]⁴⁻ polyanion above 1.4 V vs. Zn/Zn²⁺. The reversible capacity before anion decomposition is limited to half the vacancies and is due to the relative ratios of oxidized and reduced V centers. Such observations provide useful design rules for cathode materials for divalent cation based battery technologies, and highlight the necessity for a holistic interpretation of physical and electronic structural changes upon cycling.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1088/2515-7639/abe365DOIArticle
ORCID:
AuthorORCID
Martinolich, Andrew J.0000-0002-7866-9594
Ware, Skyler D.0000-0002-3249-1946
See, Kimberly A.0000-0002-0133-9693
Alternate Title:From Solid Electrolyte to Zinc Cathode: Vanadium Substitution in ZnPS3
Additional Information:© 2021 The Author(s). Published by IOP Publishing Ltd. Original content from this work may be used under the terms of the Creative Commons Attribution 4.0 license. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI. Received 20 December 2020; Accepted 4 February 2021; Published 25 February 2021. This research was supported by the Arnold and Mabel Beckman Foundation through the Beckman Young Investigator Award. The authors thank Dr FAL Laskowski for many enlightening discussions. AJM was partially supported through a postdoctoral fellowship from the Resnick Sustainability Institute at Caltech. XPS data were collected at the Molecular Materials Research Center in the Beckman Institute at Caltech.
Group:Resnick Sustainability Institute
Funders:
Funding AgencyGrant Number
Arnold and Mabel Beckman FoundationUNSPECIFIED
Resnick Sustainability InstituteUNSPECIFIED
Subject Keywords:zinc battery, zinc cathode, multivalent ionics, multivalent battery
Issue or Number:2
Record Number:CaltechAUTHORS:20210301-154055511
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210301-154055511
Official Citation:Andrew J Martinolich et al 2021 J. Phys. Mater. 4 024005
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:108259
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:01 Mar 2021 23:47
Last Modified:01 Mar 2021 23:47

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