Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation

Guo, Haoyue; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.; Liu, Ping

doi:10.1021/acsami.8b12869

Essential Role of Spinel ZnFe₂O₄ Surfaces during Lithiation

Journal Article · Wed Sep 19 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b12869· OSTI ID:1483560

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

Spinel zinc ferrite (ZnFe₂O₄) is a well-known anode material in lithium ion batteries (LIBs) due to its large theoretical capacity. However, the high potentials observed at the initial stage of lithiation observed cannot be captured using a model of Li⁺ intercalation into the stoichiometric ZnFe₂O₄ bulk. Here, using density functional theory (DFT) we report for the first time that theZnFe₂O₄ surfaces are responsible for the measured initial potentials. Among the three identified stable surfaces, ZnFeO₂-terminated ZnFe₂O₄(1 1 0), O-terminated ZnFe₂O₄(1 1 1) and Zn-terminated ZnFe₂O₄(1 1 1), both (1 1 1) surfaces display higher lithiation potentials than the (1 1 0) surface, and the estimated potentials based on Zn-terminated (1 1 1) fit well with the experimental observations, while using the models based on ZnFe₂O₄(1 1 0) and previously ZnFe₂O₄ bulk, the estimated potentials are much lower. In terms of Li⁺ diffusion, the Zn-terminated ZnFe₂O₄(1 1 1) surface is the most active, where the energetically favorable saturation of Li⁺ on the surface is able to facilitate the process. Our results provide a new strategy for the design of LIB materials, via controlling the particle shape and the associated surface characteristics thus enhancing the discharging performance.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt)

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

Grant/Contract Number:: SC0012704

OSTI ID:: 1483560

Report Number(s):: BNL--209500-2018-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 41 Vol. 10; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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