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Title: Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe2O4 in Li ion batteries: A combined XRD, EXAFS, and DFT study]

Abstract

Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe2O4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Li+ ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe2O3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe2O4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [3]
  1. Stony Brook Univ., Stony Brook, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, 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)
OSTI Identifier:
1376672
Report Number(s):
BNL-114141-2017-JA
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
SC0012704; SC0012673
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 10; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Zhang, Yiman, Pelliccione, Christopher J., Brady, Alexander B., Guo, Haoyue, Smith, Paul F., Liu, Ping, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe2O4 in Li ion batteries: A combined XRD, EXAFS, and DFT study]. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.chemmater.7b00467.
Zhang, Yiman, Pelliccione, Christopher J., Brady, Alexander B., Guo, Haoyue, Smith, Paul F., Liu, Ping, Marschilok, Amy C., Takeuchi, Kenneth J., & Takeuchi, Esther S. Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe2O4 in Li ion batteries: A combined XRD, EXAFS, and DFT study]. United States. https://doi.org/10.1021/acs.chemmater.7b00467
Zhang, Yiman, Pelliccione, Christopher J., Brady, Alexander B., Guo, Haoyue, Smith, Paul F., Liu, Ping, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Mon . "Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe2O4 in Li ion batteries: A combined XRD, EXAFS, and DFT study]". United States. https://doi.org/10.1021/acs.chemmater.7b00467. https://www.osti.gov/servlets/purl/1376672.
@article{osti_1376672,
title = {Probing the Li Insertion Mechanism of ZnFe2O4 in Li-Ion Batteries: A Combined X-Ray Diffraction, Extended X-Ray Absorption Fine Structure, and Density Functional Theory Study [Probing the Li insertion mechanism of ZnFe2O4 in Li ion batteries: A combined XRD, EXAFS, and DFT study]},
author = {Zhang, Yiman and Pelliccione, Christopher J. and Brady, Alexander B. and Guo, Haoyue and Smith, Paul F. and Liu, Ping and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {Here, we report an extensive study on fundamental properties that determine the functional electrochemistry of ZnFe2O4 spinel (theoretical capacity of 1000 mAh/g). For the first time, the reduction mechanism is followed through a combination of in situ X-ray diffraction data, synchrotron based powder diffraction, and ex-situ extended X-ray absorption fine structure allowing complete visualization of reduction products irrespective of their crystallinity. The first 0.5 electron equivalents (ee) do not significantly change the starting crystal structure. Subsequent lithiation results in migration of Zn2+ ions from 8a tetrahedral sites into vacant 16c sites. Density functional theory shows that Li+ ions insert into 16c site initially and then 8a site with further lithiation. Fe metal is formed over the next eight ee of reduction with no evidence of concurrent Zn2+ reduction to Zn metal. Despite the expected formation of LiZn alloy from the electron count, we find no evidence for this phase under the tested conditions. Additionally, upon oxidation to 3 V, we observe an FeO phase with no evidence of Fe2O3. Electrochemistry data show higher electron equivalent transfer than can be accounted for solely based on ZnFe2O4 reduction indicating excess capacity ascribed to carbon reduction or surface electrolyte interphase formation.},
doi = {10.1021/acs.chemmater.7b00467},
journal = {Chemistry of Materials},
number = 10,
volume = 29,
place = {United States},
year = {2017},
month = {4}
}

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