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Title: Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability

Abstract

Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. For lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, LixSi can bemore » processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows LixSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1394068
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 33; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Jie, Liao, Lei, Shi, Feifei, Lei, Ting, Chen, Guangxu, Pei, Allen, Sun, Jie, Yan, Kai, Zhou, Guangmin, Xie, Jin, Liu, Chong, Li, Yuzhang, Liang, Zheng, Bao, Zhenan, and Cui, Yi. Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability. United States: N. p., 2017. Web. doi:10.1021/jacs.7b05251.
Zhao, Jie, Liao, Lei, Shi, Feifei, Lei, Ting, Chen, Guangxu, Pei, Allen, Sun, Jie, Yan, Kai, Zhou, Guangmin, Xie, Jin, Liu, Chong, Li, Yuzhang, Liang, Zheng, Bao, Zhenan, & Cui, Yi. Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability. United States. doi:10.1021/jacs.7b05251.
Zhao, Jie, Liao, Lei, Shi, Feifei, Lei, Ting, Chen, Guangxu, Pei, Allen, Sun, Jie, Yan, Kai, Zhou, Guangmin, Xie, Jin, Liu, Chong, Li, Yuzhang, Liang, Zheng, Bao, Zhenan, and Cui, Yi. Wed . "Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability". United States. doi:10.1021/jacs.7b05251. https://www.osti.gov/servlets/purl/1394068.
@article{osti_1394068,
title = {Surface Fluorination of Reactive Battery Anode Materials for Enhanced Stability},
author = {Zhao, Jie and Liao, Lei and Shi, Feifei and Lei, Ting and Chen, Guangxu and Pei, Allen and Sun, Jie and Yan, Kai and Zhou, Guangmin and Xie, Jin and Liu, Chong and Li, Yuzhang and Liang, Zheng and Bao, Zhenan and Cui, Yi},
abstractNote = {Significant increases in the energy density of batteries must be achieved by exploring new materials and cell configurations. Lithium metal and lithiated silicon are two promising high-capacity anode materials. Unfortunately, both of these anodes require a reliable passivating layer to survive the serious environmental corrosion during handling and cycling. Here we developed a surface fluorination process to form a homogeneous and dense LiF coating on reactive anode materials, with in situ generated fluorine gas, by using a fluoropolymer, CYTOP, as the precursor. The process is effectively a “reaction in the beaker”, avoiding direct handling of highly toxic fluorine gas. For lithium metal, this LiF coating serves as a chemically stable and mechanically strong interphase, which minimizes the corrosion reaction with carbonate electrolytes and suppresses dendrite formation, enabling dendrite-free and stable cycling over 300 cycles with current densities up to 5 mA/cm2. Lithiated silicon can serve as either a pre-lithiation additive for existing lithium-ion batteries or a replacement for lithium metal in Li–O2 and Li–S batteries. However, lithiated silicon reacts vigorously with the standard slurry solvent N-methyl-2-pyrrolidinone (NMP), indicating it is not compatible with the real battery fabrication process. With the protection of crystalline and dense LiF coating, LixSi can be processed in anhydrous NMP with a high capacity of 2504 mAh/g. With low solubility of LiF in water, this protection layer also allows LixSi to be stable in humid air (~40% relative humidity). Furthermore, this facile surface fluorination process brings huge benefit to both the existing lithium-ion batteries and next-generation lithium metal batteries.},
doi = {10.1021/jacs.7b05251},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 139,
place = {United States},
year = {2017},
month = {7}
}

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Works referencing / citing this record:

Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries
journal, July 2019


Asymmetric behaviour of Li/Li symmetric cells for Li metal batteries
journal, January 2019

  • Koo, Dongho; Kwon, Bomee; Lee, Jeonghyeop
  • Chemical Communications, Vol. 55, Issue 65
  • DOI: 10.1039/c9cc04082j

Rational design of spontaneous reactions for protecting porous lithium electrodes in lithium–sulfur batteries
journal, July 2019


Asymmetric behaviour of Li/Li symmetric cells for Li metal batteries
journal, January 2019

  • Koo, Dongho; Kwon, Bomee; Lee, Jeonghyeop
  • Chemical Communications, Vol. 55, Issue 65
  • DOI: 10.1039/c9cc04082j