skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: New promising lithium malonatoborate salts for high voltage lithium ion batteries

Abstract

Here, three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonaoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonaoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoro malonaoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF4 and LiPF6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi0.5Mn1.5O4 (LNMO) to form effective solid electrolyte interphases (SEIs). In addition, these new salts based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi0.5Mn1.5O4 and graphite based half-cells and full cells.

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Northeast Normal Univ., Changchun (People's Republic of China)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1344276
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE

Citation Formats

Sun, Xiao -Guang, Wan, Shun, Guang, Hong Yu, Fang, Youxing, Reeves, Kimberly Shawn, Chi, Miaofang, and Dai, Sheng. New promising lithium malonatoborate salts for high voltage lithium ion batteries. United States: N. p., 2016. Web. doi:10.1039/C6TA07757A.
Sun, Xiao -Guang, Wan, Shun, Guang, Hong Yu, Fang, Youxing, Reeves, Kimberly Shawn, Chi, Miaofang, & Dai, Sheng. New promising lithium malonatoborate salts for high voltage lithium ion batteries. United States. doi:10.1039/C6TA07757A.
Sun, Xiao -Guang, Wan, Shun, Guang, Hong Yu, Fang, Youxing, Reeves, Kimberly Shawn, Chi, Miaofang, and Dai, Sheng. Thu . "New promising lithium malonatoborate salts for high voltage lithium ion batteries". United States. doi:10.1039/C6TA07757A. https://www.osti.gov/servlets/purl/1344276.
@article{osti_1344276,
title = {New promising lithium malonatoborate salts for high voltage lithium ion batteries},
author = {Sun, Xiao -Guang and Wan, Shun and Guang, Hong Yu and Fang, Youxing and Reeves, Kimberly Shawn and Chi, Miaofang and Dai, Sheng},
abstractNote = {Here, three new lithium salts, lithium difluoro-2-methyl-2-fluoromalonaoborate (LiDFMFMB), lithium difluoro-2-ethyl-2-fluoromalonaoborate (LiDFEFMB), and lithium difluoro-2-propyl-2-fluoro malonaoborate (LiDFPFMB), have been synthesized and evaluated for application in lithium ion batteries. These new salts are soluble in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.) and 1.0 M salt solutions can be easily prepared. The ionic conductivities of these new salts are close to those of LiBF4 and LiPF6. Cyclic voltammograms reveal that these new salt based electrolytes can passivate both natural graphite and high voltage spinel LiNi0.5Mn1.5O4 (LNMO) to form effective solid electrolyte interphases (SEIs). In addition, these new salts based electrolytes exhibit good cycling stability with high coulombic efficiencies in both LiNi0.5Mn1.5O4 and graphite based half-cells and full cells.},
doi = {10.1039/C6TA07757A},
journal = {Journal of Materials Chemistry. A},
number = 3,
volume = 5,
place = {United States},
year = {2016},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Synthesis and Characterization of Lithium Bis(fluoromalonato)borate for Lithium-Ion Battery Applications
journal, November 2013

  • Liao, Chen; Han, Kee Sung; Baggetto, Loïc
  • Advanced Energy Materials, Vol. 4, Issue 6
  • DOI: 10.1002/aenm.201301368

Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes
journal, January 2004

  • Xu, Kang; Lee, Unchul; Zhang, Shengshui
  • Electrochemical and Solid-State Letters, Vol. 7, Issue 9
  • DOI: 10.1149/1.1774973

A New Class of Electrochemically and Thermally Stable Lithium Salts for Lithium Battery Electrolytes
journal, January 1995

  • Barthel, J.
  • Journal of The Electrochemical Society, Vol. 142, Issue 8
  • DOI: 10.1149/1.2050048

A stable fluorinated and alkylated lithium malonatoborate salt for lithium ion battery application
journal, January 2015

  • Wan, Shun; Jiang, Xueguang; Guo, Bingkun
  • Chemical Communications, Vol. 51, Issue 48
  • DOI: 10.1039/C5CC01428J

Recent advances in the electrolytes for interfacial stability of high-voltage cathodes in lithium-ion batteries
journal, January 2015

  • Choi, Nam-Soon; Han, Jung-Gu; Ha, Se-Young
  • RSC Advances, Vol. 5, Issue 4
  • DOI: 10.1039/C4RA11575A

Graphite/Electrolyte Interface Formed in LiBOB-Based Electrolytes
journal, January 2004

  • Xu, Kang; Lee, Unchul; Zhang, Sheng S.
  • Journal of The Electrochemical Society, Vol. 151, Issue 12
  • DOI: 10.1149/1.1812732

The low temperature performance of Li-ion batteries
journal, March 2003


Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 1. From Isolated Free Ions to Conductive Aggregated Systems
journal, April 2015

  • Jankowski, Piotr; Dranka, Maciej; Żukowska, Grażyna Z.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 17
  • DOI: 10.1021/acs.jpcc.5b01352

Physicochemical Properties and Structures of Room-Temperature Ionic Liquids. 3. Variation of Cationic Structures
journal, February 2006

  • Tokuda, Hiroyuki; Ishii, Kunikazu; Susan, Md. Abu Bin Hasan
  • The Journal of Physical Chemistry B, Vol. 110, Issue 6
  • DOI: 10.1021/jp053396f

Fluorinated Electrolytes for 5-V Li-Ion Chemistry: Probing Voltage Stability of Electrolytes with Electrochemical Floating Test
journal, January 2015

  • He, Meinan; Hu, Libo; Xue, Zheng
  • Journal of The Electrochemical Society, Vol. 162, Issue 9
  • DOI: 10.1149/2.0231509jes

Network Single Ion Conductors Based on Comb-Branched Polyepoxide Ethers and Lithium Bis(allylmalonato)borate
journal, July 2004

  • Sun, Xiao-Guang; Kerr, John B.; Reeder, Craig L.
  • Macromolecules, Vol. 37, Issue 14
  • DOI: 10.1021/ma049331c

Synthesis and electrochemistry of 5V LiNi0.4Mn1.6O4 cathode materials synthesized by different methods
journal, February 2008


Polyelectrolyte Membranes Containing Lithium Malonato(difluoro)borate for Lithium-Ion Systems
conference, January 2011

  • Driscoll, Peter F.; Yang, Li; Gervais, Matthieu
  • 218th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3557699

Structural and Kinetic Characterization of Lithium Intercalation into Carbon Anodes for Secondary Lithium Batteries
journal, January 1995

  • Takami, Norio
  • Journal of The Electrochemical Society, Vol. 142, Issue 2
  • DOI: 10.1149/1.2044017

Lithium difluoro(sulfato)borate as a novel electrolyte salt for high-temperature lithium-ion batteries
journal, May 2014


Preparation of surface-modified carbonaceous thin-film electrodes by NF3 plasma and their electrochemical properties
journal, August 2005


Novel electrolyte salts based on perfluoroalkyltrifluoroborate anions
journal, September 2003


The influence of preparation conditions on electrochemical properties of LiNi0.5Mn1.5O4 thin film electrodes by PLD
journal, February 2007


Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


Bis(fluoromalonato)borate (BFMB) anion based ionic liquid as an additive for lithium-ion battery electrolytes
journal, January 2014

  • Sun, Xiao-Guang; Liao, Chen; Baggetto, Loïc
  • J. Mater. Chem. A, Vol. 2, Issue 20
  • DOI: 10.1039/C3TA14943A

Bicyclic imidazolium ionic liquids as potential electrolytes for rechargeable lithium ion batteries
journal, September 2013


Li[C[sub 2]F[sub 5]BF[sub 3]] as an Electrolyte Salt for 4 V Class Lithium-Ion Cells
journal, January 2005

  • Zhou, Zhi-Bin; Takeda, Masayuki; Fujii, Takashi
  • Journal of The Electrochemical Society, Vol. 152, Issue 2
  • DOI: 10.1149/1.1848211

Electrochemical and Infrared Studies of the Reduction of Organic Carbonates
journal, January 2001

  • Zhang, Xuerong; Kostecki, Robert; Richardson, Thomas J.
  • Journal of The Electrochemical Society, Vol. 148, Issue 12
  • DOI: 10.1149/1.1415547

Film formation in LiBOB-containing electrolytes
journal, February 2006


A Preparative Method for Perfluoroalkyltrifluoroborates and Perfluoroalkyldifluoroboranes
journal, January 2001


Generation of Cathode Passivation Films via Oxidation of Lithium Bis(oxalato) Borate on High Voltage Spinel (LiNi 0.5 Mn 1.5 O 4 )
journal, March 2014

  • Xu, Mengqing; Tsiouvaras, Nikolaos; Garsuch, Arnd
  • The Journal of Physical Chemistry C, Vol. 118, Issue 14
  • DOI: 10.1021/jp501970j

A New Class of Electrochemically and Thermally Stable Lithium Salts for Lithium Battery Electrolytes
journal, January 1996

  • Barthel, J.
  • Journal of The Electrochemical Society, Vol. 143, Issue 11
  • DOI: 10.1149/1.1837254

Synthesis and Characterization of Network Type Single Ion Conductors
journal, March 2004

  • Sun, Xiao-Guang; Reeder, Craig L.; Kerr, John B.
  • Macromolecules, Vol. 37, Issue 6
  • DOI: 10.1021/ma035690g

Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 1. Variation of Anionic Species
journal, October 2004

  • Tokuda, Hiroyuki; Hayamizu, Kikuko; Ishii, Kunikazu
  • The Journal of Physical Chemistry B, Vol. 108, Issue 42
  • DOI: 10.1021/jp047480r

Effect of electrolyte additives in improving the cycle and calendar life of graphite/Li1.1[Ni1/3Co1/3Mn1/3]0.9O2 Li-ion cells
journal, December 2007


Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study
journal, April 2011


Physicochemical properties of imidazolium-derived ionic liquids with different C-2 substitutions
journal, January 2011

  • Liao, Chen; Shao, Nan; Han, Kee Sung
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 48
  • DOI: 10.1039/c1cp22375e

Formation of the Graphite/Electrolyte Interface by Lithium Bis(oxalato)borate
journal, January 2003

  • Xu, Kang; Zhang, Shengshui; Jow, T. Richard
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 6
  • DOI: 10.1149/1.1568173

An unique lithium salt for the improved electrolyte of Li-ion battery
journal, September 2006


Impact of Lithium Bis(oxalate)borate Electrolyte Additive on the Performance of High-Voltage Spinel/Graphite Li-Ion Batteries
journal, October 2013

  • Pieczonka, Nicholas P. W.; Yang, Li; Balogh, Michael P.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 44
  • DOI: 10.1021/jp408717x

Lithium salts for advanced lithium batteries: Li–metal, Li–O 2 , and Li–S
journal, January 2015

  • Younesi, Reza; Veith, Gabriel M.; Johansson, Patrik
  • Energy & Environmental Science, Vol. 8, Issue 7
  • DOI: 10.1039/C5EE01215E

Graphite intercalation of bis(trifluoromethanesulfonyl) imide and other anions with perfluoroalkanesulfonyl substituents
journal, February 1999


Synthesis and Electrochemistry of LiNi[sub x]Mn[sub 2−x]O[sub 4]
journal, January 1997

  • Zhong, Qiming
  • Journal of The Electrochemical Society, Vol. 144, Issue 1
  • DOI: 10.1149/1.1837386

Structural Studies of Lithium 4,5-Dicyanoimidazolate–Glyme Solvates. 2. Ionic Aggregation Modes in Solution and PEO Matrix
journal, April 2015

  • Jankowski, Piotr; Dranka, Maciej; Żukowska, Grażyna Z.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 19
  • DOI: 10.1021/acs.jpcc.5b01826

Lithium difluoro(oxalato)borate: A promising salt for lithium metal based secondary batteries?
journal, March 2013


Six-Membered-Ring Malonatoborate-Based Lithium Salts as Electrolytes for Lithium Ion Batteries
conference, January 2011

  • Yang, Li; Zhang, Hanjun; Driscoll, Peter F.
  • 218th ECS Meeting, ECS Transactions
  • DOI: 10.1149/1.3589921

New boron based salts for lithium-ion batteries using conjugated ligands
journal, January 2016

  • Jankowski, P.; Wieczorek, W.; Johansson, P.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 24
  • DOI: 10.1039/C6CP02409B

New gel polyelectrolytes for rechargeable lithium batteries
journal, November 2004


Weakly Coordinating Anions, and the Exceptional Conductivity of Their Nonaqueous Solutions
journal, January 2001

  • Xu, Wu; Angell, C. Austen
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 1
  • DOI: 10.1149/1.1344281

Electrochemical characterization of electrolytes for lithium-ion batteries based on lithium difluoromono(oxalato)borate
journal, February 2011


A Novel Electrolyte Salt Additive for Lithium-Ion Batteries with Voltages Greater than 4.7 V
journal, November 2016

  • Li, Yunchao; Wan, Shun; Veith, Gabriel M.
  • Advanced Energy Materials, Vol. 7, Issue 4
  • DOI: 10.1002/aenm.201601397

Physicochemical Properties and Structures of Room Temperature Ionic Liquids. 2. Variation of Alkyl Chain Length in Imidazolium Cation
journal, April 2005

  • Tokuda, Hiroyuki; Hayamizu, Kikuko; Ishii, Kunikazu
  • The Journal of Physical Chemistry B, Vol. 109, Issue 13
  • DOI: 10.1021/jp044626d

Chemical Reactivity of PF[sub 5] and LiPF[sub 6] in Ethylene Carbonate/Dimethyl Carbonate Solutions
journal, January 2001

  • Sloop, S. E.; Pugh, J. K.; Wang, S.
  • Electrochemical and Solid-State Letters, Vol. 4, Issue 4
  • DOI: 10.1149/1.1353158

Electrochemical Intercalation of Lithium Ion within Graphite from Propylene Carbonate Solutions
journal, January 2003

  • Jeong, Soon-Ki; Inaba, Minoru; Iriyama, Yasutoshi
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 1
  • DOI: 10.1149/1.1526781

Lithium-Ion Conducting Electrolyte Salts for Lithium Batteries
journal, November 2011

  • Aravindan, Vanchiappan; Gnanaraj, Joe; Madhavi, Srinivasan
  • Chemistry - A European Journal, Vol. 17, Issue 51
  • DOI: 10.1002/chem.201101486

Chloride-Free Method to Synthesise New Ionic Liquids with Mixed Borate Anions
journal, February 2009

  • Schreiner, Christian; Amereller, Marius; Gores, Heiner J.
  • Chemistry - A European Journal, Vol. 15, Issue 10
  • DOI: 10.1002/chem.200802243

(Polyfluoroorgano)Haloboranes and (Polyfluoroorgano)Fluoroborate Salts: Preparation, nmr Spectra and Reactivity
journal, January 2002


    Works referencing / citing this record:

    Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
    journal, July 2019

    • Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
    • Angewandte Chemie, Vol. 131, Issue 45
    • DOI: 10.1002/ange.201901381

    Fluor und Lithium: Ideale Partner für Elektrolyte in wiederaufladbaren Hochleistungsbatterien
    journal, July 2019

    • Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
    • Angewandte Chemie, Vol. 131, Issue 45
    • DOI: 10.1002/ange.201901381

    Fluorine and Lithium: Ideal Partners for High‐Performance Rechargeable Battery Electrolytes
    journal, November 2019

    • Aspern, N.; Röschenthaler, G. ‐V.; Winter, M.
    • Angewandte Chemie International Edition, Vol. 58, Issue 45
    • DOI: 10.1002/anie.201901381

    Ion Dynamics in Ionic-Liquid-Based Li-Ion Electrolytes Investigated by Neutron Scattering and Dielectric Spectroscopy
    journal, September 2018


    Unsymmetrical fluorinated malonatoborate as an amphoteric additive for high-energy-density lithium-ion batteries
    journal, January 2018

    • Han, Jung-Gu; Lee, Jae Bin; Cha, Aming
    • Energy & Environmental Science, Vol. 11, Issue 6
    • DOI: 10.1039/c8ee00372f

    A promising bulky anion based lithium borate salt for lithium metal batteries
    journal, January 2018

    • Qiao, Lixin; Cui, Zili; Chen, Bingbing
    • Chemical Science, Vol. 9, Issue 14
    • DOI: 10.1039/c8sc00041g