In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of LixNa1.5–x VOPO 4 F 0.5
Abstract
Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li+/Na+ substitution during solvothermal ion-exchange synthesis of LixNa1.5-xVOPO4F0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na+ by Li+, leading to peculiar Na+/Li+/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.
- Authors:
-
[4];
[3]
- Brookhaven National Lab. (BNL), Upton, NY (United States); Seoul National Univ. (Korea, Republic of)
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Seoul National Univ. (Korea, Republic of)
- Koreal Atomic Energy Research Inst. (Korea, Republic of)
- Brookhaven National Lab. (BNL), Upton, NY (United States); Koreal Atomic Energy Research Inst. (Korea, Republic of)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1389228
- Alternate Identifier(s):
- OSTI ID: 1413935
- Report Number(s):
- BNL-114157-2017-JA; BNL-114529-2017-JA
Journal ID: ISSN 0002-7863; TRN: US1702362
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 139; Journal Issue: 36; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE
Citation Formats
Park, Young-Uk, Bai, Jianming, Wang, Liping, Yoon, Gabin, Zhang, Wei, Kim, Hyungsub, Lee, Seongsu, Kim, Sung-Wook, Looney, J. Patrick, Kang, Kisuk, and Wang, Feng. In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of LixNa1.5–x VOPO 4 F 0.5. United States: N. p., 2017.
Web. doi:10.1021/jacs.7b05302.
Park, Young-Uk, Bai, Jianming, Wang, Liping, Yoon, Gabin, Zhang, Wei, Kim, Hyungsub, Lee, Seongsu, Kim, Sung-Wook, Looney, J. Patrick, Kang, Kisuk, & Wang, Feng. In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of LixNa1.5–x VOPO 4 F 0.5. United States. https://doi.org/10.1021/jacs.7b05302
Park, Young-Uk, Bai, Jianming, Wang, Liping, Yoon, Gabin, Zhang, Wei, Kim, Hyungsub, Lee, Seongsu, Kim, Sung-Wook, Looney, J. Patrick, Kang, Kisuk, and Wang, Feng. Tue .
"In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of LixNa1.5–x VOPO 4 F 0.5". United States. https://doi.org/10.1021/jacs.7b05302. https://www.osti.gov/servlets/purl/1389228.
@article{osti_1389228,
title = {In Situ Tracking Kinetic Pathways of Li + /Na + Substitution during Ion-Exchange Synthesis of LixNa1.5–x VOPO 4 F 0.5},
author = {Park, Young-Uk and Bai, Jianming and Wang, Liping and Yoon, Gabin and Zhang, Wei and Kim, Hyungsub and Lee, Seongsu and Kim, Sung-Wook and Looney, J. Patrick and Kang, Kisuk and Wang, Feng},
abstractNote = {Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li+/Na+ substitution during solvothermal ion-exchange synthesis of LixNa1.5-xVOPO4F0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na+ by Li+, leading to peculiar Na+/Li+/vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.},
doi = {10.1021/jacs.7b05302},
journal = {Journal of the American Chemical Society},
number = 36,
volume = 139,
place = {United States},
year = {Tue Aug 29 00:00:00 EDT 2017},
month = {Tue Aug 29 00:00:00 EDT 2017}
}
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