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Title: Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries

Abstract

A series of lithium difluoro-2-fluoro-2-alkyl-malonatoborate salts have been used as additives in conventional 1.0 M LiPF 6/ethylene carbonate (EC)-dimethyl carbonate (DMC)-diethyl carbonate (DEC) (1-1-1, by v) electrolyte for high voltage LiNi 0.5Mn 1.5O 4 (LNMO) batteries. Cyclic voltammograms (CVs) reveals that the electrolytes with additives can significantly suppress the co-intercalation of solvents into the graphene layers during the first cycle, simply because of their sacrificial reductions on the surface of the graphite electrode above 1.0 V vs Li/Li +. In addition, electrochemical floating test shows less oxidation current in the electrolytes with additives at voltages above 5.0 V, proving good oxidation protection by the additives. More importantly, the presence of additives can effectively increase the first cycle coulombic efficiencies and long cycling stability in LNMO based half-cells and full cells. SEM and XPS survey of the cycled anode and cathode electrodes provide evidence for the formation of passivation layers. Lastly, these passivation layers can also protect the surface of current collector from corrosion, confirming that these new salts are effective additives in conventional electrolytes for high-voltage lithium ion batteries.

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [5]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Bredesen Center for Interdisciplinary Research and Graduate Education
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1394292
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 40; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Lithium malonatoborate salts; Solid Electrolyte Interfaces (SEI); LiNi1.5Mn0.5O4 (LNMO); Additives; High-Voltage batteries

Citation Formats

Li, Yunchao, Veith, Gabriel M., Browning, Katie L., Chen, Jihua, Hensley, Dale K., Paranthaman, Mariappan Parans, Dai, Sheng, and Sun, Xiao-Guang. Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries. United States: N. p., 2017. Web. doi:10.1016/j.nanoen.2017.07.051.
Li, Yunchao, Veith, Gabriel M., Browning, Katie L., Chen, Jihua, Hensley, Dale K., Paranthaman, Mariappan Parans, Dai, Sheng, & Sun, Xiao-Guang. Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries. United States. doi:10.1016/j.nanoen.2017.07.051.
Li, Yunchao, Veith, Gabriel M., Browning, Katie L., Chen, Jihua, Hensley, Dale K., Paranthaman, Mariappan Parans, Dai, Sheng, and Sun, Xiao-Guang. Tue . "Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries". United States. doi:10.1016/j.nanoen.2017.07.051.
@article{osti_1394292,
title = {Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries},
author = {Li, Yunchao and Veith, Gabriel M. and Browning, Katie L. and Chen, Jihua and Hensley, Dale K. and Paranthaman, Mariappan Parans and Dai, Sheng and Sun, Xiao-Guang},
abstractNote = {A series of lithium difluoro-2-fluoro-2-alkyl-malonatoborate salts have been used as additives in conventional 1.0 M LiPF6/ethylene carbonate (EC)-dimethyl carbonate (DMC)-diethyl carbonate (DEC) (1-1-1, by v) electrolyte for high voltage LiNi0.5Mn1.5O4 (LNMO) batteries. Cyclic voltammograms (CVs) reveals that the electrolytes with additives can significantly suppress the co-intercalation of solvents into the graphene layers during the first cycle, simply because of their sacrificial reductions on the surface of the graphite electrode above 1.0 V vs Li/Li+. In addition, electrochemical floating test shows less oxidation current in the electrolytes with additives at voltages above 5.0 V, proving good oxidation protection by the additives. More importantly, the presence of additives can effectively increase the first cycle coulombic efficiencies and long cycling stability in LNMO based half-cells and full cells. SEM and XPS survey of the cycled anode and cathode electrodes provide evidence for the formation of passivation layers. Lastly, these passivation layers can also protect the surface of current collector from corrosion, confirming that these new salts are effective additives in conventional electrolytes for high-voltage lithium ion batteries.},
doi = {10.1016/j.nanoen.2017.07.051},
journal = {Nano Energy},
issn = {2211-2855},
number = ,
volume = 40,
place = {United States},
year = {2017},
month = {8}
}