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Title: A first principles study of spinel ZnFe 2O 4 for electrode materials in lithium-ion batteries

Abstract

Zinc ferrite (ZnFe 2O 4) is a perspective lithium ion battery material, owing to its large theoretical capacity (1000 mAh/g). Here, we report a density functional study of the discharge process at early stage from ZnFe 2O 4 up to LixZnFe2O4 (x = 2), aiming to provide fundamental understanding of the mechanism. According to our calculations, with x increasing up to 1 the intercalation of Li+ ions prefer octahedral 16c sites, which is accompanied by Zn 2+ ion displacement from tetrahedral 8a sites to 16c sites starting at x = 0.25 and the gain in stability; while the stability decreases for 1 < x ≤ 2 due to the occupation of Li+ ions at the less active tetrahedral 8a/48f/8b sites. The open-circuit voltages estimated based on the structures of stable intermediates identified by the DFT calculations are in good agreement with the experimental values. Our results highlight the importance of the interplay among Li, O 2-, Fe 3+ and Zn 2+ in enabling the high performance as LIB materials.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [2]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1466612
Report Number(s):
[BNL-207958-2018-JAAM]
[Journal ID: ISSN 1463-9076; PPCPFQ]
Grant/Contract Number:  
[SC0012704]
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
[Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 38]; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Guo, Haoyue, Zhang, Yiman, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. A first principles study of spinel ZnFe2O4 for electrode materials in lithium-ion batteries. United States: N. p., 2017. Web. doi:10.1039/C7CP04590E.
Guo, Haoyue, Zhang, Yiman, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., & Liu, Ping. A first principles study of spinel ZnFe2O4 for electrode materials in lithium-ion batteries. United States. doi:10.1039/C7CP04590E.
Guo, Haoyue, Zhang, Yiman, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. Wed . "A first principles study of spinel ZnFe2O4 for electrode materials in lithium-ion batteries". United States. doi:10.1039/C7CP04590E. https://www.osti.gov/servlets/purl/1466612.
@article{osti_1466612,
title = {A first principles study of spinel ZnFe2O4 for electrode materials in lithium-ion batteries},
author = {Guo, Haoyue and Zhang, Yiman and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Liu, Ping},
abstractNote = {Zinc ferrite (ZnFe2O4) is a perspective lithium ion battery material, owing to its large theoretical capacity (1000 mAh/g). Here, we report a density functional study of the discharge process at early stage from ZnFe2O4 up to LixZnFe2O4 (x = 2), aiming to provide fundamental understanding of the mechanism. According to our calculations, with x increasing up to 1 the intercalation of Li+ ions prefer octahedral 16c sites, which is accompanied by Zn2+ ion displacement from tetrahedral 8a sites to 16c sites starting at x = 0.25 and the gain in stability; while the stability decreases for 1 < x ≤ 2 due to the occupation of Li+ ions at the less active tetrahedral 8a/48f/8b sites. The open-circuit voltages estimated based on the structures of stable intermediates identified by the DFT calculations are in good agreement with the experimental values. Our results highlight the importance of the interplay among Li, O2-, Fe3+ and Zn2+ in enabling the high performance as LIB materials.},
doi = {10.1039/C7CP04590E},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = [38],
volume = [19],
place = {United States},
year = {2017},
month = {9}
}

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