Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite
Abstract
Spinel transition metal oxides (TMOs) have emerged as promising anode materials for lithium-ion batteries. It has been shown that reducing their particle size to nanoscale dimensions benefits overall electrochemical performance. Here, we use in situ transmission electron microscopy to probe the lithiation behavior of spinel ZnFe2O4 as a function of particle size. We have found that ZnFe2O4 undergoes an intercalation-to-conversion reaction sequence, with the initial intercalation process being size dependent. Larger ZnFe2O4 particles (40 nm) follow a two-phase intercalation reaction. In contrast, a solid-solution transformation dominates the early stages of discharge when the particle size is about 6–9 nm. Using a thermodynamic analysis, we find that the size-dependent kinetics originate from the interfacial energy between the two phases. Furthermore, the conversion reaction in both large and small particles favors {111} planes and follows a core-shell reaction mode. Finally, these results elucidate the intrinsic mechanism that permits fast reaction kinetics in smaller nanoparticles.
- Authors:
-
[2];
[4];
[2];
[6];
[8]
- State Univ. of New York (SUNY), Plattsburgh, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering
- Brookhaven National Lab. (BNL), Upton, NY (United States). Dept. of Condensed Matter Physics
- State Univ. of New York (SUNY), Plattsburgh, NY (United States); Stony Brook Univ., NY (United States). Dept. of Chemistry
- Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program and Dept. of Mechanical Engineering
- State Univ. of New York (SUNY), Plattsburgh, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering, and Dept. of Chemistry; Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- State Univ. of New York (SUNY), Plattsburgh, NY (United States); Stony Brook Univ., NY (United States). Dept. of Materials Science and Chemical Engineering, and Dept. of Chemistry
- Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2mt); Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1493184
- Report Number(s):
- BNL-211237-2019-JAAM
Journal ID: ISSN 2041-1723
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Communications
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Li, Jing, Meng, Qingping, Zhang, Yiman, Peng, Lele, Yu, Guihua, Marschilok, Amy C., Wu, Lijun, Su, Dong, Takeuchi, Kenneth J., Takeuchi, Esther S., Zhu, Yimei, and Stach, Eric A. Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite. United States: N. p., 2019.
Web. doi:10.1038/s41467-018-07831-5.
Li, Jing, Meng, Qingping, Zhang, Yiman, Peng, Lele, Yu, Guihua, Marschilok, Amy C., Wu, Lijun, Su, Dong, Takeuchi, Kenneth J., Takeuchi, Esther S., Zhu, Yimei, & Stach, Eric A. Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite. United States. https://doi.org/10.1038/s41467-018-07831-5
Li, Jing, Meng, Qingping, Zhang, Yiman, Peng, Lele, Yu, Guihua, Marschilok, Amy C., Wu, Lijun, Su, Dong, Takeuchi, Kenneth J., Takeuchi, Esther S., Zhu, Yimei, and Stach, Eric A. Wed .
"Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite". United States. https://doi.org/10.1038/s41467-018-07831-5. https://www.osti.gov/servlets/purl/1493184.
@article{osti_1493184,
title = {Size-dependent kinetics during non-equilibrium lithiation of nano-sized zinc ferrite},
author = {Li, Jing and Meng, Qingping and Zhang, Yiman and Peng, Lele and Yu, Guihua and Marschilok, Amy C. and Wu, Lijun and Su, Dong and Takeuchi, Kenneth J. and Takeuchi, Esther S. and Zhu, Yimei and Stach, Eric A.},
abstractNote = {Spinel transition metal oxides (TMOs) have emerged as promising anode materials for lithium-ion batteries. It has been shown that reducing their particle size to nanoscale dimensions benefits overall electrochemical performance. Here, we use in situ transmission electron microscopy to probe the lithiation behavior of spinel ZnFe2O4 as a function of particle size. We have found that ZnFe2O4 undergoes an intercalation-to-conversion reaction sequence, with the initial intercalation process being size dependent. Larger ZnFe2O4 particles (40 nm) follow a two-phase intercalation reaction. In contrast, a solid-solution transformation dominates the early stages of discharge when the particle size is about 6–9 nm. Using a thermodynamic analysis, we find that the size-dependent kinetics originate from the interfacial energy between the two phases. Furthermore, the conversion reaction in both large and small particles favors {111} planes and follows a core-shell reaction mode. Finally, these results elucidate the intrinsic mechanism that permits fast reaction kinetics in smaller nanoparticles.},
doi = {10.1038/s41467-018-07831-5},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {Wed Jan 09 00:00:00 EST 2019},
month = {Wed Jan 09 00:00:00 EST 2019}
}
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Surface Coating Constraint Induced Self-Discharging of Silicon Nanoparticles as Anodes for Lithium Ion Batteries
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Kinetic Phase Evolution of Spinel Cobalt Oxide during Lithiation
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Electrospun Core–Shell Fibers for Robust Silicon Nanoparticle-Based Lithium Ion Battery Anodes
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Understanding materials challenges for rechargeable ion batteries with in situ transmission electron microscopy
journal, August 2017
- Yuan, Yifei; Amine, Khalil; Lu, Jun
- Nature Communications, Vol. 8, Issue 1
Kinetics of non-equilibrium lithium incorporation in LiFePO4
journal, July 2011
- Malik, Rahul; Zhou, Fei; Ceder, G.
- Nature Materials, Vol. 10, Issue 8
Origin of additional capacities in metal oxide lithium-ion battery electrodes
journal, November 2013
- Hu, Yan-Yan; Liu, Zigeng; Nam, Kyung-Wan
- Nature Materials, Vol. 12, Issue 12
Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries
journal, January 2011
- Ji, Liwen; Lin, Zhan; Alcoutlabi, Mataz
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Optimal and near‐optimal filters in high‐resolution electron microscopy
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- Kilaas, R.
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Spinel Anodes for Lithium-Ion Batteries
journal, January 1994
- Ferg, E.; Gummow, R. J.; de Kock, A.
- Journal of The Electrochemical Society, Vol. 141, Issue 11, p. L147-L150
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