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

Title: 4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries

Abstract

In this study we characterize 4-(trimethylsilyl) morpholine (TMSML) as a multifunctional electrolyte additive in Li1.03(Ni0.5Mn0.3Co0.2)0.97O2 (NMC532)//Graphite cells operating at 3-4.4 V. This additive completely prevents the hydrolysis of LiPF6 caused by traces of water in a carbonate electrolyte, both ex and in situ. It also inhibits oxidative decomposition of electrolyte on the energized cathode, impedes the formation of electrically insulating deposits on the cathode surface, decreases transition metal loss from the cathode in aged cells, improves the discharge capacity retention, and decreases the rise of cell resistance during aging. We trace these beneficial functions to the ease of nucleophilic substitution and the N-Si bond dissociation in the TMSML. Our results suggest that TMSML could be a promising electrolyte additive in the high voltage lithium ion batteries.

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Office of Science (SC)
OSTI Identifier:
1603742
Alternate Identifier(s):
OSTI ID: 1632159
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society (Online) Journal Volume: 167 Journal Issue: 7; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Yang, Jianzhong, Shkrob, Ilya, Liu, Kewei, Connell, Justin, Dietz Rago, Nancy L., Zhang, Zhengcheng, and Liao, Chen. 4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries. United States: N. p., 2020. Web. doi:10.1149/1945-7111/ab7a9e.
Yang, Jianzhong, Shkrob, Ilya, Liu, Kewei, Connell, Justin, Dietz Rago, Nancy L., Zhang, Zhengcheng, & Liao, Chen. 4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries. United States. doi:https://doi.org/10.1149/1945-7111/ab7a9e
Yang, Jianzhong, Shkrob, Ilya, Liu, Kewei, Connell, Justin, Dietz Rago, Nancy L., Zhang, Zhengcheng, and Liao, Chen. Wed . "4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries". United States. doi:https://doi.org/10.1149/1945-7111/ab7a9e.
@article{osti_1603742,
title = {4-(Trimethylsilyl) Morpholine as a Multifunctional Electrolyte Additive in High Voltage Lithium Ion Batteries},
author = {Yang, Jianzhong and Shkrob, Ilya and Liu, Kewei and Connell, Justin and Dietz Rago, Nancy L. and Zhang, Zhengcheng and Liao, Chen},
abstractNote = {In this study we characterize 4-(trimethylsilyl) morpholine (TMSML) as a multifunctional electrolyte additive in Li1.03(Ni0.5Mn0.3Co0.2)0.97O2 (NMC532)//Graphite cells operating at 3-4.4 V. This additive completely prevents the hydrolysis of LiPF6 caused by traces of water in a carbonate electrolyte, both ex and in situ. It also inhibits oxidative decomposition of electrolyte on the energized cathode, impedes the formation of electrically insulating deposits on the cathode surface, decreases transition metal loss from the cathode in aged cells, improves the discharge capacity retention, and decreases the rise of cell resistance during aging. We trace these beneficial functions to the ease of nucleophilic substitution and the N-Si bond dissociation in the TMSML. Our results suggest that TMSML could be a promising electrolyte additive in the high voltage lithium ion batteries.},
doi = {10.1149/1945-7111/ab7a9e},
journal = {Journal of the Electrochemical Society (Online)},
number = 7,
volume = 167,
place = {United States},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1149/1945-7111/ab7a9e

Save / Share:

Works referenced in this record:

A review on electrolyte additives for lithium-ion batteries
journal, November 2006


Improved Interfacial Properties of MCMB Electrode by 1-(Trimethylsilyl)imidazole as New Electrolyte Additive To Suppress LiPF 6 Decomposition
journal, January 2017

  • Wotango, Aselefech Sorsa; Su, Wei-Nien; Leggesse, Ermias Girma
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 3
  • DOI: 10.1021/acsami.6b13105

Decomposition reaction of LiPF6-based electrolytes for lithium ion cells
journal, June 2006


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


An accelerated calendar and cycle life study of Li-ion cells
journal, October 2001


High Voltage LiNi 0.5 Mn 0.3 Co 0.2 O 2 /Graphite Cell Cycled at 4.6 V with a FEC/HFDEC-Based Electrolyte
journal, April 2017

  • He, Meinan; Su, Chi-Cheung; Feng, Zhenxing
  • Advanced Energy Materials, Vol. 7, Issue 15
  • DOI: 10.1002/aenm.201700109

Comparison of Metal Ion Dissolutions from Lithium Ion Battery Cathodes
journal, January 2006

  • Choi, W.; Manthiram, A.
  • Journal of The Electrochemical Society, Vol. 153, Issue 9
  • DOI: 10.1149/1.2219710

Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries
journal, April 2015

  • Han, Jung-Gu; Lee, Sung Jun; Lee, Jaegi
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 15
  • DOI: 10.1021/acsami.5b01770

Interpreting High Precision Coulometry Results on Li-ion Cells
journal, January 2011

  • Smith, A. J.; Burns, J. C.; Xiong, D.
  • Journal of The Electrochemical Society, Vol. 158, Issue 10
  • DOI: 10.1149/1.3625232

Editors' Choice—Practical Assessment of Anionic Redox in Li-Rich Layered Oxide Cathodes: A Mixed Blessing for High Energy Li-Ion Batteries
journal, January 2016

  • Assat, Gaurav; Delacourt, Charles; Corte, Daniel Alves Dalla
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0531614jes

Dehydration Rather Than HF Capture Explains Performance Improvements of Li-Ion Cells by Ceramic Nanoparticles
journal, July 2019

  • Rodrigues, Marco-Tulio F.; Liao, Chen; Kalaga, Kaushik
  • ACS Applied Energy Materials, Vol. 2, Issue 8
  • DOI: 10.1021/acsaem.9b00976

A causal study of the capacity fading of Li1.01Mn1.99O4 cathode at 80°C, and the suppressing substances of its fading
journal, August 2001


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


Understanding Long-Term Cycling Performance of Li 1.2 Ni 0.15 Mn 0.55 Co 0.1 O 2 –Graphite Lithium-Ion Cells
journal, January 2013

  • Li, Y.; Bettge, M.; Polzin, B.
  • Journal of The Electrochemical Society, Vol. 160, Issue 5
  • DOI: 10.1149/2.002305jes

Lifetime limit of tris(trimethylsilyl) phosphite as electrolyte additive for high voltage lithium ion batteries
journal, January 2016

  • Qi, Xin; Tao, Liang; Hahn, Hendrik
  • RSC Advances, Vol. 6, Issue 44
  • DOI: 10.1039/C6RA06555D

Enabling High-Energy, High-Voltage Lithium-Ion Cells: Standardization of Coin-Cell Assembly, Electrochemical Testing, and Evaluation of Full Cells
journal, January 2016

  • Long, Brandon R.; Rinaldo, Steven G.; Gallagher, Kevin G.
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0691614jes

High capacity silicon nitride-based composite anodes for lithium ion batteries
journal, January 2014

  • de Guzman, Rhet C.; Yang, Jinho; Ming-Cheng Cheng, Mark
  • J. Mater. Chem. A, Vol. 2, Issue 35
  • DOI: 10.1039/C4TA02596B

Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach
journal, October 2017


Improving the electrochemical performance of high voltage spinel cathode at elevated temperature by a novel electrolyte additive
journal, January 2016


Effect of heptamethyldisilazane as an additive on the stability performance of LiMn2O4 cathode for lithium-ion battery
journal, April 2009


The mechanism of HF formation in LiPF6 based organic carbonate electrolytes
journal, January 2012


A Bifunctional Electrolyte Additive for High-Voltage LiNi 0.5 Mn 1.5 O 4 Positive Electrodes
journal, March 2019

  • Lee, Tae Jin; Soon, Jiyong; Chae, Seulki
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 12
  • DOI: 10.1021/acsami.8b19009

A bifunctional electrolyte additive for H 2 O/HF scavenging and enhanced graphite/LiNi 0.5 Co 0.2 Mn 0.3 O 2 cell performance at a high voltage
journal, January 2018

  • Zhou, Rong; Huang, Jianxing; Lai, Shaobo
  • Sustainable Energy & Fuels, Vol. 2, Issue 7
  • DOI: 10.1039/C8SE00064F

Photo electron transfer induced desilylation of N , N -bis(trimethylsilyl)aminodibenzoborole to aminodibenzoborole
journal, January 2019

  • Keck, Constanze; Maichle-Mössmer, Cäcilia; Bettinger, Holger F.
  • Chemical Communications, Vol. 55, Issue 52
  • DOI: 10.1039/C9CC03415C

Development of novel lithium borate additives for designed surface modification of high voltage LiNi 0.5 Mn 1.5 O 4 cathodes
journal, January 2016

  • Xu, Mengqing; Zhou, Liu; Dong, Yingnan
  • Energy & Environmental Science, Vol. 9, Issue 4
  • DOI: 10.1039/C5EE03360H

Thermal Decomposition of LiPF[sub 6]-Based Electrolytes for Lithium-Ion Batteries
journal, January 2005

  • Campion, Christopher L.; Li, Wentao; Lucht, Brett L.
  • Journal of The Electrochemical Society, Vol. 152, Issue 12
  • DOI: 10.1149/1.2083267