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Title: Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O 2 Batteries

Authors:
 [1];  [1];  [2];  [3];  [2];  [4];  [4];  [5];  [2];  [1]
  1. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA
  2. Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland WA 99354 USA
  3. Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA, Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan 689-798 South Korea
  4. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland WA 99354 USA
  5. Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology, Ulsan 689-798 South Korea
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400619
Grant/Contract Number:
DEAC02-05CH11231; DEAC02-98CH10886; AC05-76RLO1830
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 7; Journal Issue: 14; Related Information: CHORUS Timestamp: 2017-10-20 15:10:30; Journal ID: ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Liu, Bin, Xu, Wu, Yan, Pengfei, Kim, Sun Tai, Engelhard, Mark H., Sun, Xiuliang, Mei, Donghai, Cho, Jaephil, Wang, Chong-Min, and Zhang, Ji-Guang. Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O 2 Batteries. Germany: N. p., 2017. Web. doi:10.1002/aenm.201602605.
Liu, Bin, Xu, Wu, Yan, Pengfei, Kim, Sun Tai, Engelhard, Mark H., Sun, Xiuliang, Mei, Donghai, Cho, Jaephil, Wang, Chong-Min, & Zhang, Ji-Guang. Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O 2 Batteries. Germany. doi:10.1002/aenm.201602605.
Liu, Bin, Xu, Wu, Yan, Pengfei, Kim, Sun Tai, Engelhard, Mark H., Sun, Xiuliang, Mei, Donghai, Cho, Jaephil, Wang, Chong-Min, and Zhang, Ji-Guang. Wed . "Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O 2 Batteries". Germany. doi:10.1002/aenm.201602605.
@article{osti_1400619,
title = {Stabilization of Li Metal Anode in DMSO-Based Electrolytes via Optimization of Salt-Solvent Coordination for Li-O 2 Batteries},
author = {Liu, Bin and Xu, Wu and Yan, Pengfei and Kim, Sun Tai and Engelhard, Mark H. and Sun, Xiuliang and Mei, Donghai and Cho, Jaephil and Wang, Chong-Min and Zhang, Ji-Guang},
abstractNote = {},
doi = {10.1002/aenm.201602605},
journal = {Advanced Energy Materials},
number = 14,
volume = 7,
place = {Germany},
year = {Wed Mar 08 00:00:00 EST 2017},
month = {Wed Mar 08 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/aenm.201602605

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  • The conventional DMSO-based electrolyte (1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in DMSO) is unstable against the Li metal anode and therefore cannot be used directly in practical Li-O2 batteries. Here, we demonstrate that a highly concentrated electrolyte based on LiTFSI in DMSO (with a molar ratio of 1:3) can greatly improve the stability of the Li metal anode against DMSO and significantly improve the cycling stability of Li-O2 batteries. This highly concentrated electrolyte contains no free DMSO solvent molecules, but only complexes of (TFSI–)a-Li+-(DMSO)b (where a + b = 4), and thus enhances their stability with Li metal anodes. In addition,more » such salt-solvent complexes have higher Gibbs activation energy barriers than the free DMSO solvent molecules, indicating improved stability of the electrolyte against the attack of superoxide radical anions. Therefore, the stability of this highly concentrated electrolyte at both Li metal anodes and carbon-based air electrodes has been greatly enhanced, resulting in improved cyclic stability of Li-O2 batteries. The fundamental stability of the electrolyte with free-solvent against the chemical and electrochemical reactions can also be used to enhance the stability of other electrochemical systems.« less
  • Highlights: • Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} nanocomposites with high grain boundary density were synthesized. • {sup 7}Li NMR and impedance spectroscopy shows high Li-ion mobility in nanocomposites. • The shape of charge/discharge curves changes for nanocomposites. • Influence of particle size on cycling performance of lithium titanates was shown. • Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} nanocomposite exhibits good cycling performance and rate capability. - Abstract: Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} nanocomposites are synthesized by a sol-gel method. The size of Li{sub 4}Ti{sub 5}O{sub 12} and TiO{sub 2} particles is of 4–5 and 7–10 nm, respectively. The obtained materials aremore » characterized by XRD, SEM, HRTEM and BET. Ion mobility of the composites and their performance as anode materials for lithium-ion batteries are studied. According to the conductivity and {sup 7}Li NMR data, Li{sup +} mobility is much higher in the Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} nanocomposites as compared with that in pure Li{sub 4}Ti{sub 5}O{sub 12}. For Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} nanocomposites, marked changes in the charge–discharge curves are observed; charge–discharge rate and effective capacity at a high cycling rate are shown to increase. During the first cycle, charge capacity of these materials surpasses the theoretical capacity of Li{sub 4}Ti{sub 5}O{sub 12}. However, this parameter decreases sharply with cycling, whereas the discharge capacity remains almost unchanged. This phenomenon is attributed to the solid electrolyte interphase formation due to a partial electrolyte reduction on the Li{sub 4}Ti{sub 5}O{sub 12}/TiO{sub 2} composite surface.« less
  • The electrochemical parameters of compact disk cells with cathodes of Li{sub 1+{ital x}}V{sub 3}O{sub 8}, LiCr{sub 0.9}V{sub 0.1}S{sub 2}, and electrolytes based on cyclic ethers, are studied. In this paper it is shown that the decrease of discharge time from 10 to 1.3 h has but a small effect on cathode utilization, which drops from 80% to about 70% for both cathode materials. The polarization resistances of freshly deposited Li, from electrolytes of ethers, and their mixtures with ethylene carbonate, are identical. Continuous cycling tests with maximum cathode utilization in the electrolyte of composition 1.5 {ital M} LiAsF{sub 6}/2MeTHF/THF (1:1)more » 0.2% 2MeF demonstrate a cycling efficiency of 96--97% for Li. A lower efficiency of about 94% is obtained in ethylene carbonate containing electrolytes. It is suggested that an increase in the thickness of the passive film formed on the Li electrode is responsible for the capacity decay at the end of the cycling life. The rate of self-discharge at room temperature for a fully charged cell is about 5--8% per month. This self-discharge is attributed to the Li electrode, which is passivated during storage in the ether-based electrolytes.« less