Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation
Abstract
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.
- Authors:
-
[1];
[1];
[1];
[2];
[2]
- Stony Brook Univ., NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1483560
- Report Number(s):
- BNL-209500-2018-JAAM
Journal ID: ISSN 1944-8244
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 41; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; ZnFe2O4; DFT; surface stability; Li absorption; Li diffusion; Li-ion batteries
Citation Formats
Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation. United States: N. p., 2018.
Web. doi:10.1021/acsami.8b12869.
Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., & Liu, Ping. Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation. United States. https://doi.org/10.1021/acsami.8b12869
Guo, Haoyue, Marschilok, Amy C., Takeuchi, Kenneth J., Takeuchi, Esther S., and Liu, Ping. Wed .
"Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation". United States. https://doi.org/10.1021/acsami.8b12869. https://www.osti.gov/servlets/purl/1483560.
@article{osti_1483560,
title = {Essential Role of Spinel ZnFe2O4 Surfaces during Lithiation},
author = {Guo, Haoyue and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Liu, Ping},
abstractNote = {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.},
doi = {10.1021/acsami.8b12869},
journal = {ACS Applied Materials and Interfaces},
number = 41,
volume = 10,
place = {United States},
year = {Wed Sep 19 00:00:00 EDT 2018},
month = {Wed Sep 19 00:00:00 EDT 2018}
}
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Figures / Tables:
Figure 1: Phase diagram and the corresponding structures of stable terminations of ZnFe2O4 (1 0 0), (1 1 0) and (1 1 1) surfaces.
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Works referencing / citing this record:
A network of porous carbon/ZnCo 2 O 4 nanotubes derived from shell-hybridized worm-like micelles for lithium storage
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Rationalization of Diversity in Spinel MgFe 2 O 4 Surfaces
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Density Functional Theory for Battery Materials
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Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.