Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance

Rynearson, Leah; Rodrigo, Nuwanthi D.; Jayawardana, Chamithri; Lucht, Brett L.

doi:10.1149/1945-7111/ac6455

Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance

Journal Article · Sun Apr 17 20:00:00 EDT 2022 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac6455· OSTI ID:1863476

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An electrolyte consisting of lithium nitrate (LiNO ₃ ) and lithium difluoro(oxalato)borate (LiDFOB) in ethylene carbonate (EC), ethylmethyl carbonate (EMC), and triethyl phosphate (TEP) is used to improve the long-term cycling stability of silicon anodes. TEP was selected for its ability to dissolve LiNO ₃ in carbonates to a concentration of ∼0.2 M. The large amount of LiNO ₃ combined with the LiDFOB salt leads to a capacity retention of 87.1% after one hundred cycles due to the formation of a relatively stable solid electrolyte interphase (SEI). Ex-situ surface analysis reveals that the SEI consists of oxalates, lithium alkyl carbonates, borates, and nitrate reduction products. By selecting two components which are preferentially reduced (LiNO ₃ and LiDFOB), the SEI is able to inhibit continuous solvent decomposition and allows for improved electrochemical cycling for pure silicon anodes.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0021392

OSTI ID:: 1863476

Alternate ID(s):: OSTI ID: 1861211
OSTI ID: 2589063
OSTI ID: 1980880

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 4 Vol. 169; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (37)

Lithium Nitrate Solvation Chemistry in Carbonate Electrolyte Sustains High-Voltage Lithium Metal Batteries Yan, Chong; Yao, Yu-Xing; Chen, Xiang Angewandte Chemie International Edition, Vol. 57, Issue 43 https://doi.org/10.1002/anie.201807034	journal	September 2018
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Role of LiNO3 in rechargeable lithium/sulfur battery Zhang, Sheng S. Electrochimica Acta, Vol. 70 https://doi.org/10.1016/j.electacta.2012.03.081	journal	May 2012
Understanding the thermal instability of fluoroethylene carbonate in LiPF 6 -based electrolytes for lithium ion batteries Kim, Koeun; Park, Inbok; Ha, Se-Young Electrochimica Acta, Vol. 225 https://doi.org/10.1016/j.electacta.2016.12.126	journal	January 2017
Generation and Evolution of the Solid Electrolyte Interphase of Lithium-Ion Batteries Heiskanen, Satu Kristiina; Kim, Jongjung; Lucht, Brett L. Joule, Vol. 3, Issue 10 https://doi.org/10.1016/j.joule.2019.08.018	journal	October 2019
A highly safe battery with a non-flammable triethyl-phosphate-based electrolyte Matsumoto, Kazuaki; Inoue, Kazuhiko; Utsugi, Koji Journal of Power Sources, Vol. 273 https://doi.org/10.1016/j.jpowsour.2014.09.086	journal	January 2015
Influence of inactive electrode components on degradation phenomena in nano-Si electrodes for Li-ion batteries Jeschull, Fabian; Lindgren, Fredrik; Lacey, Matthew J. Journal of Power Sources, Vol. 325 https://doi.org/10.1016/j.jpowsour.2016.06.059	journal	September 2016
What Makes Fluoroethylene Carbonate Different? Shkrob, Ilya A.; Wishart, James F.; Abraham, Daniel P. The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b03591	journal	June 2015
Evolution of the Solid–Electrolyte Interphase on Carbonaceous Anodes Visualized by Atomic-Resolution Cryogenic Electron Microscopy Huang, William; Attia, Peter M.; Wang, Hansen Nano Letters, Vol. 19, Issue 8 https://doi.org/10.1021/acs.nanolett.9b01515	journal	July 2019
Systematic Investigation of Binders for Silicon Anodes: Interactions of Binder with Silicon Particles and Electrolytes and Effects of Binders on Solid Electrolyte Interphase Formation Nguyen, Cao Cuong; Yoon, Taeho; Seo, Daniel M. ACS Applied Materials & Interfaces, Vol. 8, Issue 19 https://doi.org/10.1021/acsami.6b03357	journal	May 2016
The Critical Role of Fluoroethylene Carbonate in the Gassing of Silicon Anodes for Lithium-Ion Batteries Schiele, Alexander; Breitung, Ben; Hatsukade, Toru ACS Energy Letters, Vol. 2, Issue 10 https://doi.org/10.1021/acsenergylett.7b00619	journal	September 2017
Role of Surface Oxides in the Formation of Solid–Electrolyte Interphases at Silicon Electrodes for Lithium-Ion Batteries Schroder, Kjell W.; Dylla, Anthony G.; Harris, Stephen J. ACS Applied Materials & Interfaces, Vol. 6, Issue 23 https://doi.org/10.1021/am506517j	journal	November 2014
A Rechargeable Li–O ₂ Battery Using a Lithium Nitrate/ N , N -Dimethylacetamide Electrolyte Walker, Wesley; Giordani, Vincent; Uddin, Jasim Journal of the American Chemical Society, Vol. 135, Issue 6 https://doi.org/10.1021/ja311518s	journal	January 2013
Syntheses and Characterization of Lithium Alkyl Mono- and Dicarbonates as Components of Surface Films in Li-Ion Batteries Xu, Kang; Zhuang, Guorong V.; Allen, Jan L. The Journal of Physical Chemistry B, Vol. 110, Issue 15 https://doi.org/10.1021/jp0601522	journal	March 2006
Examining Solid Electrolyte Interphase Formation on Crystalline Silicon Electrodes: Influence of Electrochemical Preparation and Ambient Exposure Conditions Schroder, Kjell W.; Celio, Hugo; Webb, Lauren J. The Journal of Physical Chemistry C, Vol. 116, Issue 37 https://doi.org/10.1021/jp307372m	journal	September 2012
Silicon Solid Electrolyte Interphase (SEI) of Lithium Ion Battery Characterized by Microscopy and Spectroscopy Nie, Mengyun; Abraham, Daniel P.; Chen, Yanjing The Journal of Physical Chemistry C, Vol. 117, Issue 26 https://doi.org/10.1021/jp404155y	journal	June 2013
Effect of Fluoroethylene Carbonate (FEC) on the Performance and Surface Chemistry of Si-Nanowire Li-Ion Battery Anodes Etacheri, Vinodkumar; Haik, Ortal; Goffer, Yossi Langmuir, Vol. 28, Issue 1 https://doi.org/10.1021/la203712s	journal	December 2011
Exceptional Electrochemical Performance of Si-Nanowires in 1,3-Dioxolane Solutions: A Surface Chemical Investigation Etacheri, Vinodkumar; Geiger, Uzi; Gofer, Yossi Langmuir, Vol. 28, Issue 14 https://doi.org/10.1021/la300306v	journal	March 2012
Solubility-mediated sustained release enabling nitrate additive in carbonate electrolytes for stable lithium metal anode Liu, Yayuan; Lin, Dingchang; Li, Yuzhang Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-06077-5	journal	September 2018
Non-flammable electrolytes with high salt-to-solvent ratios for Li-ion and Li-metal batteries Zeng, Ziqi; Murugesan, Vijayakumar; Han, Kee Sung Nature Energy, Vol. 3, Issue 8 https://doi.org/10.1038/s41560-018-0196-y	journal	July 2018
The critical role of lithium nitrate in the gas evolution of lithium–sulfur batteries Jozwiuk, Anna; Berkes, Balázs B.; Weiß, Thomas Energy & Environmental Science, Vol. 9, Issue 8 https://doi.org/10.1039/C6EE00789A	journal	January 2016
Introduction to x-ray photoelectron spectroscopy Stevie, Fred A.; Donley, Carrie L. Journal of Vacuum Science & Technology A, Vol. 38, Issue 6 https://doi.org/10.1116/6.0000412	journal	December 2020
Electrochemical and Infrared Studies of the Reduction of Organic Carbonates Zhang, Xuerong; Kostecki, Robert; Richardson, Thomas J. Journal of The Electrochemical Society, Vol. 148, Issue 12 https://doi.org/10.1149/1.1415547	journal	January 2001
An Attempt to Formulate Nonflammable Lithium Ion Electrolytes with Alkyl Phosphates and Phosphazenes Xu, Kang; Ding, Michael S.; Zhang, Shengshui Journal of The Electrochemical Society, Vol. 149, Issue 5 https://doi.org/10.1149/1.1467946	journal	January 2002
Structural Changes in Silicon Anodes during Lithium Insertion/Extraction Obrovac, M. N.; Christensen, Leif Electrochemical and Solid-State Letters, Vol. 7, Issue 5 https://doi.org/10.1149/1.1652421	journal	January 2004
Study of SEI Layer Formed on Graphite Anodes in PC/LiBOB Electrolyte Using IR Spectroscopy Zhuang, G. V.; Xu, K.; Jow, T. R. Electrochemical and Solid-State Letters, Vol. 7, Issue 8 https://doi.org/10.1149/1.1756855	journal	January 2004
Failure Modes of Silicon Powder Negative Electrode in Lithium Secondary Batteries Ryu, Ji Heon; Kim, Jae Woo; Sung, Yung-Eun Electrochemical and Solid-State Letters, Vol. 7, Issue 10, p. A306-A309 https://doi.org/10.1149/1.1792242	journal	January 2004
A Comparative Study of Synthetic Graphite and Li Electrodes in Electrolyte Solutions Based on Ethylene Carbonate-Dimethyl Carbonate Mixtures Aurbach, D. Journal of The Electrochemical Society, Vol. 143, Issue 12 https://doi.org/10.1149/1.1837300	journal	January 1996
Lithium Difluoro(oxalato)borate as Salt for Lithium-Ion Batteries Chen, Zonghai; Liu, J.; Amine, K. Electrochemical and Solid-State Letters, Vol. 10, Issue 3 https://doi.org/10.1149/1.2409743	journal	January 2007
Investigation of Lithium Tetrafluorooxalatophosphate [LiPF[sub 4](C[sub 2]O[sub 4])] as a Lithium-Ion Battery Electrolyte for Elevated Temperature Performance Xu, Mengqing; Xiao, Ang; Li, Weishan Journal of The Electrochemical Society, Vol. 157, Issue 1 https://doi.org/10.1149/1.3258290	journal	January 2010
Perspective—Structure and Stability of the Solid Electrolyte Interphase on Silicon Anodes of Lithium-ion Batteries Kim, Jongjung; Chae, Oh B.; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 168, Issue 3 https://doi.org/10.1149/1945-7111/abe984	journal	March 2021
Investigation of the Disproportionation Reactions and Equilibrium of Lithium Difluoro(Oxalato) Borate (LiDFOB) Zhou, Liu; Li, Wentao; Xu, Mengqing Electrochemical and Solid-State Letters, Vol. 14, Issue 11 https://doi.org/10.1149/2.016111esl	journal	January 2011
Role of Lithium Salt on Solid Electrolyte Interface (SEI) Formation and Structure in Lithium Ion Batteries Nie, Mengyun; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 161, Issue 6 https://doi.org/10.1149/2.054406jes	journal	January 2014
Development of Electrolytes for Si-Graphite Composite Electrodes Nguyen, Cao Cuong; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 165, Issue 10 https://doi.org/10.1149/2.0621810jes	journal	January 2018
Comparative Study of Fluoroethylene Carbonate and Vinylene Carbonate for Silicon Anodes in Lithium Ion Batteries Nguyen, Cao Cuong; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 161, Issue 12 https://doi.org/10.1149/2.0731412jes	journal	January 2014
Reduction Reactions of Electrolyte Salts for Lithium Ion Batteries: LiPF ₆ , LiBF ₄ , LiDFOB, LiBOB, and LiTFSI Parimalam, Bharathy S.; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 165, Issue 2 https://doi.org/10.1149/2.0901802jes	journal	January 2018
Using Triethyl Phosphate to Increase the Solubility of LiNO ₃ in Carbonate Electrolytes for Improving the Performance of the Lithium Metal Anode Brown, Zachary L.; Heiskanen, Satu; Lucht, Brett L. Journal of The Electrochemical Society, Vol. 166, Issue 12 https://doi.org/10.1149/2.0991912jes	journal	January 2019

Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance

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Electrolytes Containing Triethyl Phosphate Solubilized Lithium Nitrate for Improved Silicon Anode Performance

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