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Title: Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions

Metal oxides, such as Fe 3O 4, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple-electron transfer reactions leading to high capacity in Fe 3O 4, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O 2–) and cations (Li +, Fe 3+/Fe 2+) using multiple synchrotron X-ray and electron-beam techniques, in combination with ab-initio calculations. Results from this study provide the first experimental evidence that the cubic-close-packed (ccp) O-anion array in Fe 3O 4 is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O-anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock-salt-like phases (Li xFe 3O 4; 0 < x < 2), then into a cation-segregated phase (Li 2O•FeO), and finally converting into metallic Fe and Li 2O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO-like phases. Lastly, these results may offer new insights into the structure-determined ionic transport and electrochemical reactions inmore » metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.« less
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [3] ;  [4] ;  [3] ;  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. American Physical Society, Ridge NY (United States)
  3. Stony Brook Univ., Stony Brook, NY (United States)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., Stony Brook, NY (United States)
Publication Date:
Report Number(s):
BNL-111956-2016-JA
Journal ID: ISSN 1614-6832; YN0100000
Grant/Contract Number:
SC00112704
Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 10; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; batteries; high-capacity electrodes; multiple-electron transfer reactions; ionic transport; magnetite
OSTI Identifier:
1341518

Zhang, Wei, Bock, David C., Pelliccione, Christopher J., Li, Yan, Wu, Lijun, Zhu, Yimei, Marschilok, Amy. C., Takeuchi, Esther S., Takeuchi, Kenneth J., and Wang, Feng. Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions. United States: N. p., Web. doi:10.1002/aenm.201502471.
Zhang, Wei, Bock, David C., Pelliccione, Christopher J., Li, Yan, Wu, Lijun, Zhu, Yimei, Marschilok, Amy. C., Takeuchi, Esther S., Takeuchi, Kenneth J., & Wang, Feng. Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions. United States. doi:10.1002/aenm.201502471.
Zhang, Wei, Bock, David C., Pelliccione, Christopher J., Li, Yan, Wu, Lijun, Zhu, Yimei, Marschilok, Amy. C., Takeuchi, Esther S., Takeuchi, Kenneth J., and Wang, Feng. 2016. "Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions". United States. doi:10.1002/aenm.201502471. https://www.osti.gov/servlets/purl/1341518.
@article{osti_1341518,
title = {Insights into ionic transport and structural changes in magnetite during multiple-electron transfer reactions},
author = {Zhang, Wei and Bock, David C. and Pelliccione, Christopher J. and Li, Yan and Wu, Lijun and Zhu, Yimei and Marschilok, Amy. C. and Takeuchi, Esther S. and Takeuchi, Kenneth J. and Wang, Feng},
abstractNote = {Metal oxides, such as Fe3O4, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple-electron transfer reactions leading to high capacity in Fe3O4, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O2–) and cations (Li+, Fe3+/Fe2+) using multiple synchrotron X-ray and electron-beam techniques, in combination with ab-initio calculations. Results from this study provide the first experimental evidence that the cubic-close-packed (ccp) O-anion array in Fe3O4 is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O-anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock-salt-like phases (LixFe3O4; 0 < x < 2), then into a cation-segregated phase (Li2O•FeO), and finally converting into metallic Fe and Li2O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO-like phases. Lastly, these results may offer new insights into the structure-determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.},
doi = {10.1002/aenm.201502471},
journal = {Advanced Energy Materials},
number = 10,
volume = 6,
place = {United States},
year = {2016},
month = {3}
}