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]

Zhang, Yiman; Pelliccione, Christopher J.; Brady, Alexander B.; Guo, Haoyue; Smith, Paul F.; Liu, Ping; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

doi:10.1021/acs.chemmater.7b00467

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]

Journal Article · Mon Apr 24 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b00467· OSTI ID:1376672

Zhang, Yiman ^[1]; Pelliccione, Christopher J. ^[2]; Brady, Alexander B. ^[1]; Guo, Haoyue ^[1]; Smith, Paul F. ^[1]; ^[2]; ^[1]; Takeuchi, Kenneth J. ^[1]; ^[3]

Stony Brook Univ., Stony Brook, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Stony Brook Univ., Stony Brook, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704; SC0012673

OSTI ID:: 1376672

Alternate ID(s):: OSTI ID: 1368319

Report Number(s):: BNL--114141-2017-JA

Journal Information:: Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 10 Vol. 29; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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