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Title: Insight into Ca-Substitution Effects on O3-Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium-Ion Batteries Application

Abstract

O3-type NaNi1/3Fe1/3Mn1/3O2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na+ diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na1-xCax/2NFM (x=0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na1-xCax/2NFM samples show single alpha-NaFeO2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na0.9Ca0.05Ni1/3Fe1/3Mn1/3O2 (Na0.9Ca0.05NFM) cathode delivers a capacity of 116.3 mAh g-1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na0.9Ca0.05NFM cathode during cycling. Compared to NaNMF, the Na0.9Ca0.05NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na0.9Ca0.05NFM makes it a promising material for practical applications in sodium-ion batteries.

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [2];  [2];  [1];  [1];  [2];  [1]
  1. Shanghai Jiao Tong Univ. (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Natural Science Foundation of China (NNSFC); National Key Research and Development Program of China; USDOE
OSTI Identifier:
1463686
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Small
Additional Journal Information:
Journal Volume: 14; Journal Issue: 21; Journal ID: ISSN 1613-6810
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Ca-substitution; layered sodium transition metal oxide; sodium-ion batteries

Citation Formats

Sun, Liqi, Xie, Yingying, Liao, Xiao-Zhen, Wang, Hong, Tan, Guoqiang, Chen, Zonghai, Ren, Yang, Gim, Jihyeon, Tang, Wan, He, Yu-Shi, Amine, Khalil, and Ma, Zi-Feng. Insight into Ca-Substitution Effects on O3-Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium-Ion Batteries Application. United States: N. p., 2018. Web. doi:10.1002/smll.201704523.
Sun, Liqi, Xie, Yingying, Liao, Xiao-Zhen, Wang, Hong, Tan, Guoqiang, Chen, Zonghai, Ren, Yang, Gim, Jihyeon, Tang, Wan, He, Yu-Shi, Amine, Khalil, & Ma, Zi-Feng. Insight into Ca-Substitution Effects on O3-Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium-Ion Batteries Application. United States. doi:10.1002/smll.201704523.
Sun, Liqi, Xie, Yingying, Liao, Xiao-Zhen, Wang, Hong, Tan, Guoqiang, Chen, Zonghai, Ren, Yang, Gim, Jihyeon, Tang, Wan, He, Yu-Shi, Amine, Khalil, and Ma, Zi-Feng. Wed . "Insight into Ca-Substitution Effects on O3-Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium-Ion Batteries Application". United States. doi:10.1002/smll.201704523. https://www.osti.gov/servlets/purl/1463686.
@article{osti_1463686,
title = {Insight into Ca-Substitution Effects on O3-Type NaNi1/3Fe1/3Mn1/3O2 Cathode Materials for Sodium-Ion Batteries Application},
author = {Sun, Liqi and Xie, Yingying and Liao, Xiao-Zhen and Wang, Hong and Tan, Guoqiang and Chen, Zonghai and Ren, Yang and Gim, Jihyeon and Tang, Wan and He, Yu-Shi and Amine, Khalil and Ma, Zi-Feng},
abstractNote = {O3-type NaNi1/3Fe1/3Mn1/3O2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na+ diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na1-xCax/2NFM (x=0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na1-xCax/2NFM samples show single alpha-NaFeO2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na0.9Ca0.05Ni1/3Fe1/3Mn1/3O2 (Na0.9Ca0.05NFM) cathode delivers a capacity of 116.3 mAh g-1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na0.9Ca0.05NFM cathode during cycling. Compared to NaNMF, the Na0.9Ca0.05NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na0.9Ca0.05NFM makes it a promising material for practical applications in sodium-ion batteries.},
doi = {10.1002/smll.201704523},
journal = {Small},
number = 21,
volume = 14,
place = {United States},
year = {2018},
month = {4}
}

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