Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe2O4)
Abstract
Zinc ferrite, ZnFe2O4 (ZFO), is a promising electrode material for next generation Li-ion batteries because of its high theoretical capacity and low environmental impact. In this report, synthetic control of crystallite size from the nanometer to submicron scale enabled probing of the relationships between ZFO size and electrochemical behavior. Here, a facile two-step coprecipitation and annealing preparation method was used to prepare ZFO with controlled sizes ranging ~9 to >200 nm. Complementary synchrotron and electron microscopy techniques were used to characterize the series of materials. Increasing the annealing temperature increased crystallinity and decreased microstrain, while local structural ordering was maintained independent of crystallite size. Electrochemical characterization revealed that the smaller sized materials delivered higher capacities during initial lithiation. Larger sized particles exhibited a lack of distinct electrochemical signatures above 1.0 V, suggesting that the longer diffusion length associated with greater crystallite size causes the lithiation process to proceed via non discrete lithium insertion, cation migration, and conversion processes. Notably, larger particles exhibited enhanced electrochemical reversibility over 50 cycles, with capacity retention improving from <20% to >40% at C/2 cycling rate. This intriguing result was probed through x-ray absorption spectroscopy (XAS) and x-ray photoelectron spectroscopy (XPS) measurements of the cycled electrodes.more »
- Authors:
-
- Stony Brook Univ., NY (United States)
- Stony Brook Univ., NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1809063
- Report Number(s):
- BNL-221838-2021-JAAM
Journal ID: ISSN 0957-4484
- Grant/Contract Number:
- SC0012704; SC0012673
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nanotechnology
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 37; Journal ID: ISSN 0957-4484
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Tallman, Killian R., West, Patrick J., Yan, Shan, Yao, Shanshan, Quilty, Calvin D., Wang, Feng, Marschilok, Amy C., Bock, David C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe2O4). United States: N. p., 2021.
Web. doi:10.1088/1361-6528/ac09a9.
Tallman, Killian R., West, Patrick J., Yan, Shan, Yao, Shanshan, Quilty, Calvin D., Wang, Feng, Marschilok, Amy C., Bock, David C., Takeuchi, Kenneth J., & Takeuchi, Esther S. Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe2O4). United States. https://doi.org/10.1088/1361-6528/ac09a9
Tallman, Killian R., West, Patrick J., Yan, Shan, Yao, Shanshan, Quilty, Calvin D., Wang, Feng, Marschilok, Amy C., Bock, David C., Takeuchi, Kenneth J., and Takeuchi, Esther S. Fri .
"Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe2O4)". United States. https://doi.org/10.1088/1361-6528/ac09a9. https://www.osti.gov/servlets/purl/1809063.
@article{osti_1809063,
title = {Structural and electrochemical investigation of crystallite size controlled zinc ferrite (ZnFe2O4)},
author = {Tallman, Killian R. and West, Patrick J. and Yan, Shan and Yao, Shanshan and Quilty, Calvin D. and Wang, Feng and Marschilok, Amy C. and Bock, David C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {Zinc ferrite, ZnFe2O4 (ZFO), is a promising electrode material for next generation Li-ion batteries because of its high theoretical capacity and low environmental impact. In this report, synthetic control of crystallite size from the nanometer to submicron scale enabled probing of the relationships between ZFO size and electrochemical behavior. Here, a facile two-step coprecipitation and annealing preparation method was used to prepare ZFO with controlled sizes ranging ~9 to >200 nm. Complementary synchrotron and electron microscopy techniques were used to characterize the series of materials. Increasing the annealing temperature increased crystallinity and decreased microstrain, while local structural ordering was maintained independent of crystallite size. Electrochemical characterization revealed that the smaller sized materials delivered higher capacities during initial lithiation. Larger sized particles exhibited a lack of distinct electrochemical signatures above 1.0 V, suggesting that the longer diffusion length associated with greater crystallite size causes the lithiation process to proceed via non discrete lithium insertion, cation migration, and conversion processes. Notably, larger particles exhibited enhanced electrochemical reversibility over 50 cycles, with capacity retention improving from <20% to >40% at C/2 cycling rate. This intriguing result was probed through x-ray absorption spectroscopy (XAS) and x-ray photoelectron spectroscopy (XPS) measurements of the cycled electrodes. XAS revealed that the larger crystallite size materials do not completely convert to Fe0 during the first lithiation and that independent of size, delithiation results in the formation of nanocrystalline FeO and ZnO phases rather than ZnFe2O4. After 20 cycles, the larger crystallites showed reversibility between partially oxidized FeO in the charged state and Fe0 in the discharged state, while the smaller crystallite size material was electrochemically inactive as Fe0. XPS analysis revealed more significant solid electrolyte interphase (SEI) formation on the cycled electrodes utilizing ZFO with smaller crystallite size. This finding suggests that excessive SEI buildup on the smaller sized, higher surface area ZFO particles contributes to their reduced electrochemical reversibility relative to the larger crystallite size materials.},
doi = {10.1088/1361-6528/ac09a9},
journal = {Nanotechnology},
number = 37,
volume = 32,
place = {United States},
year = {Fri Jun 25 00:00:00 EDT 2021},
month = {Fri Jun 25 00:00:00 EDT 2021}
}
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