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Title: Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes

Abstract

Metal fluorides and oxides can store multiple lithium ions through conversion chemistry to enable high-energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage profiles and the consequent low-energy efficiency (<80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the FeF3 electrode is kinetic in nature. It is the result of ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically active phases (i.e., compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency ofmore » lithium-ion batteries based on conversion chemistry.« less

Authors:
 [1];  [2];  [3];  [1];  [3];  [2];  [1]
+ Show Author Affiliations
  1. Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53705, United States
  2. Department of Materials Science and Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, United States
  3. Sustainable Energy Technology Division, Brookhaven National Laboratory, Upton, New York 11973, United States
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1238408
Alternate Identifier(s):
OSTI ID: 1354467
Report Number(s):
BNL-112984-2016-JA
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC00112704; DMR-1106184; DMR-1508558; AC02-98CH10886
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 138 Journal Issue: 8; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Hysteresis; Lithiation; Electrodes; Extended X-ray absorption fine structure; Materials

Citation Formats

Li, Linsen, Jacobs, Ryan, Gao, Peng, Gan, Liyang, Wang, Feng, Morgan, Dane, and Jin, Song. Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes. United States: N. p., 2016. Web. doi:10.1021/jacs.6b00061.
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Li, Linsen, Jacobs, Ryan, Gao, Peng, Gan, Liyang, Wang, Feng, Morgan, Dane, & Jin, Song. Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes. United States. https://doi.org/10.1021/jacs.6b00061
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Li, Linsen, Jacobs, Ryan, Gao, Peng, Gan, Liyang, Wang, Feng, Morgan, Dane, and Jin, Song. Fri . "Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes". United States. https://doi.org/10.1021/jacs.6b00061.
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@article{osti_1238408,
title = {Origins of Large Voltage Hysteresis in High-Energy-Density Metal Fluoride Lithium-Ion Battery Conversion Electrodes},
author = {Li, Linsen and Jacobs, Ryan and Gao, Peng and Gan, Liyang and Wang, Feng and Morgan, Dane and Jin, Song},
abstractNote = {Metal fluorides and oxides can store multiple lithium ions through conversion chemistry to enable high-energy-density lithium-ion batteries. However, their practical applications have been hindered by an unusually large voltage hysteresis between charge and discharge voltage profiles and the consequent low-energy efficiency (<80%). The physical origins of such hysteresis are rarely studied and poorly understood. Here we employ in situ X-ray absorption spectroscopy, transmission electron microscopy, density functional theory calculations, and galvanostatic intermittent titration technique to first correlate the voltage profile of iron fluoride (FeF3), a representative conversion electrode material, with evolution and spatial distribution of intermediate phases in the electrode. The results reveal that, contrary to conventional belief, the phase evolution in the electrode is symmetrical during discharge and charge. However, the spatial evolution of the electrochemically active phases, which is controlled by reaction kinetics, is different. We further propose that the voltage hysteresis in the FeF3 electrode is kinetic in nature. It is the result of ohmic voltage drop, reaction overpotential, and different spatial distributions of electrochemically active phases (i.e., compositional inhomogeneity). Therefore, the large hysteresis can be expected to be mitigated by rational design and optimization of material microstructure and electrode architecture to improve the energy efficiency of lithium-ion batteries based on conversion chemistry.},
doi = {10.1021/jacs.6b00061},
journal = {Journal of the American Chemical Society},
number = 8,
volume = 138,
place = {United States},
year = {Fri Feb 19 00:00:00 EST 2016},
month = {Fri Feb 19 00:00:00 EST 2016}
}
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https://doi.org/10.1021/jacs.6b00061
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