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Title: Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries

Abstract

The development of highly reversible multielectron reaction per redox center in sodium super ionic conductor-structured cathode materials is desired to improve the energy density of sodium-ion batteries. Here, we investigated more than one-electron storage of Na in Na3VCr(PO4)3. Combining a series of advanced characterization techniques such as ex situ 51V solid-state nuclear magnetic resonance, X-ray absorption near-edge structure, and in situ X-ray diffraction, we reveal that V3+/V4+ and V4+/V5+ redox couples in the materials can be accessed, leading to a 1.5-electron reaction. It is also found that a light change on the local electronic and structural states or phase change could be observed after the first cycle, resulting in the fast capacity fade at room temperature. As a result, we also showed that the irreversibility of the phase changes could be largely suppressed at low temperature, thus leading to a much improved electrochemical performance.

Authors:
 [1];  [2];  [1];  [1];  [1];  [1];  [1];  [3];  [2];  [4];  [1];  [1]
  1. Xiamen Univ., Xiamen (People's Republic of China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. National High Magnetic Field Lab., Tallahassee, FL (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States); Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Key Research and Development Program of China; National Natural Science Foundation of China (NSFC); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1460535
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 50; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; NASICON; NMR; XAS; low temperature; multielectron reaction; sodium-ion batteries; structural evolution

Citation Formats

Liu, Rui, Xu, Guiliang, Zheng, Shiyao, Zheng, Guorui, Gong, Zhenliang, Li, Yixiao, Kruskop, Elizaveta, Fu, Riqiang, Chen, Zonghai, Amine, Khalil, Yang, Yong, and Li, Qi. Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries. United States: N. p., 2017. Web. doi:10.1021/acsami.7b13018.
Liu, Rui, Xu, Guiliang, Zheng, Shiyao, Zheng, Guorui, Gong, Zhenliang, Li, Yixiao, Kruskop, Elizaveta, Fu, Riqiang, Chen, Zonghai, Amine, Khalil, Yang, Yong, & Li, Qi. Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries. United States. https://doi.org/10.1021/acsami.7b13018
Liu, Rui, Xu, Guiliang, Zheng, Shiyao, Zheng, Guorui, Gong, Zhenliang, Li, Yixiao, Kruskop, Elizaveta, Fu, Riqiang, Chen, Zonghai, Amine, Khalil, Yang, Yong, and Li, Qi. Wed . "Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries". United States. https://doi.org/10.1021/acsami.7b13018. https://www.osti.gov/servlets/purl/1460535.
@article{osti_1460535,
title = {Exploring Highly Reversible 1.5-Electron Reactions (V3+/V4+/V5+) in Na3VCr(PO4)3 Cathode for Sodium-Ion Batteries},
author = {Liu, Rui and Xu, Guiliang and Zheng, Shiyao and Zheng, Guorui and Gong, Zhenliang and Li, Yixiao and Kruskop, Elizaveta and Fu, Riqiang and Chen, Zonghai and Amine, Khalil and Yang, Yong and Li, Qi},
abstractNote = {The development of highly reversible multielectron reaction per redox center in sodium super ionic conductor-structured cathode materials is desired to improve the energy density of sodium-ion batteries. Here, we investigated more than one-electron storage of Na in Na3VCr(PO4)3. Combining a series of advanced characterization techniques such as ex situ 51V solid-state nuclear magnetic resonance, X-ray absorption near-edge structure, and in situ X-ray diffraction, we reveal that V3+/V4+ and V4+/V5+ redox couples in the materials can be accessed, leading to a 1.5-electron reaction. It is also found that a light change on the local electronic and structural states or phase change could be observed after the first cycle, resulting in the fast capacity fade at room temperature. As a result, we also showed that the irreversibility of the phase changes could be largely suppressed at low temperature, thus leading to a much improved electrochemical performance.},
doi = {10.1021/acsami.7b13018},
journal = {ACS Applied Materials and Interfaces},
number = 50,
volume = 9,
place = {United States},
year = {Wed Nov 22 00:00:00 EST 2017},
month = {Wed Nov 22 00:00:00 EST 2017}
}

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Three Electron Reversible Redox Reaction in Sodium Vanadium Chromium Phosphate as a High‐Energy‐Density Cathode for Sodium‐Ion Batteries
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