Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries

Cao, Xia; Gao, Peiyuan; Ren, Xiaodi; Zou, Lianfeng; Engelhard, Mark H.; Matthews, Bethany E.; Hu, Jiangtao; Niu, Chaojiang; Liu, Dianying; Arey, Bruce W.; Wang, Chongmin; Xiao, Jie; Liu, Jun; Xu, Wu; Zhang, Jiguang

doi:10.1073/pnas.2020357118

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries

Journal Article · Tue Mar 02 04:00:00 EST 2021 · Proceedings of the National Academy of Sciences (PNAS).

DOI:https://doi.org/10.1073/pnas.2020357118· OSTI ID:1778835

Cao, Xia ^[1]; Gao, Peiyuan ^[1]; Ren, Xiaodi ^[1]; Zou, Lianfeng ^[1]; ^[1]; Matthews, Bethany E. ^[1]; Hu, Jiangtao ^[1]; Niu, Chaojiang ^[1]; Liu, Dianying ^[1]; Arey, Bruce W. ^[1]; ^[1]; Xiao, Jie ^[1]; Liu, Jun ^[2]; ^[1]; ^[1]

BATTELLE (PACIFIC NW LAB)
MULTIPLE CONTRACTORS

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next generation high-density energy storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structure. Types of fluorinated co-solvents used in LHCEs are investigated here in searching for the most suitable diluent for high concentration electrolytes (HCEs). Non-solvating solvents (including fluorinated ethers, fluorinated borate and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through co-participation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery-performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1778835

Report Number(s):: PNNL-SA-154541

Journal Information:: Proceedings of the National Academy of Sciences (PNAS)., Journal Name: Proceedings of the National Academy of Sciences (PNAS). Journal Issue: 9 Vol. 118

Country of Publication:: United States

Language:: English

References (27)

Extremely Stable Sodium Metal Batteries Enabled by Localized High-Concentration Electrolytes Zheng, Jianming; Chen, Shuru; Zhao, Wengao ACS Energy Letters, Vol. 3, Issue 2 https://doi.org/10.1021/acsenergylett.7b01213	journal	January 2018
High‐Fluorinated Electrolytes for Li–S Batteries Zheng, Jing; Ji, Guangbin; Fan, Xiulin Advanced Energy Materials, Vol. 9, Issue 16 https://doi.org/10.1002/aenm.201803774	journal	February 2019
Superconcentrated electrolytes for a high-voltage lithium-ion battery Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12032	journal	June 2016
Lithium Metal Anodes with Nonaqueous Electrolytes Zhang, Ji-Guang; Xu, Wu; Xiao, Jie Chemical Reviews, Vol. 120, Issue 24 https://doi.org/10.1021/acs.chemrev.0c00275	journal	November 2020
High‐Performance Silicon Anodes Enabled By Nonflammable Localized High‐Concentration Electrolytes Jia, Haiping; Zou, Lianfeng; Gao, Peiyuan Advanced Energy Materials, Vol. 9, Issue 31 https://doi.org/10.1002/aenm.201900784	journal	July 2019
High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes Chen, Shuru; Zheng, Jianming; Mei, Donghai Advanced Materials, Vol. 30, Issue 21 https://doi.org/10.1002/adma.201706102	journal	March 2018
Role of inner solvation sheath within salt–solvent complexes in tailoring electrode/electrolyte interphases for lithium metal batteries Ren, Xiaodi; Gao, Peiyuan; Zou, Lianfeng Proceedings of the National Academy of Sciences, Vol. 117, Issue 46 https://doi.org/10.1073/pnas.2010852117	journal	November 2020
Lithium metal anodes for rechargeable batteries Xu, Wu; Wang, Jiulin; Ding, Fei Energy Environ. Sci., Vol. 7, Issue 2 https://doi.org/10.1039/C3EE40795K	journal	January 2014
Localized High-Concentration Sulfone Electrolytes for High-Efficiency Lithium-Metal Batteries Ren, Xiaodi; Chen, Shuru; Lee, Hongkyung Chem, Vol. 4, Issue 8 https://doi.org/10.1016/j.chempr.2018.05.002	journal	August 2018
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
Enabling High-Voltage Lithium-Metal Batteries under Practical Conditions Ren, Xiaodi; Zou, Lianfeng; Cao, Xia Joule, Vol. 3, Issue 7 https://doi.org/10.1016/j.joule.2019.05.006	journal	July 2019
Nonflammable Electrolytes for Lithium Ion Batteries Enabled by Ultraconformal Passivation Interphases Cao, Xia; Xu, Yaobin; Zhang, Linchao ACS Energy Letters, Vol. 4, Issue 10 https://doi.org/10.1021/acsenergylett.9b01926	journal	September 2019
High-Efficiency Lithium Metal Batteries with Fire-Retardant Electrolytes Chen, Shuru; Zheng, Jianming; Yu, Lu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.05.002	journal	August 2018
Stable cycling of high-voltage lithium metal batteries in ether electrolytes Jiao, Shuhong; Ren, Xiaodi; Cao, Ruiguo Nature Energy, Vol. 3, Issue 9 https://doi.org/10.1038/s41560-018-0199-8	journal	July 2018
Advances and issues in developing salt-concentrated battery electrolytes Yamada, Yuki; Wang, Jianhui; Ko, Seongjae Nature Energy https://doi.org/10.1038/s41560-019-0336-z	journal	March 2019
A Localized High-Concentration Electrolyte with Optimized Solvents and Lithium Difluoro(oxalate)borate Additive for Stable Lithium Metal Batteries Yu, Lu; Chen, Shuru; Lee, Hongkyung ACS Energy Letters, Vol. 3, Issue 9 https://doi.org/10.1021/acsenergylett.8b00935	journal	July 2018
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries Xu, Kang Chemical Reviews, Vol. 104, Issue 10, p. 4303-4418 https://doi.org/10.1021/cr030203g	journal	October 2004
Fluorine-donating electrolytes enable highly reversible 5-V-class Li metal batteries Suo, Liumin; Xue, Weijiang; Gobet, Mallory Proceedings of the National Academy of Sciences, Vol. 115, Issue 6 https://doi.org/10.1073/pnas.1712895115	journal	January 2018
Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids Jorgensen, William L.; Maxwell, David S.; Tirado-Rives, Julian Journal of the American Chemical Society, Vol. 118, Issue 45 https://doi.org/10.1021/ja9621760	journal	January 1996
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review Cheng, Xin-Bing; Zhang, Rui; Zhao, Chen-Zi Chemical Reviews, Vol. 117, Issue 15 https://doi.org/10.1021/acs.chemrev.7b00115	journal	July 2017
Monolithic solid–electrolyte interphases formed in fluorinated orthoformate-based electrolytes minimize Li depletion and pulverization Cao, Xia; Ren, Xiaodi; Zou, Lianfeng Nature Energy, Vol. 4, Issue 9 https://doi.org/10.1038/s41560-019-0464-5	journal	September 2019
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
High rate and stable cycling of lithium metal anode Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7362	journal	February 2015
Solid–Liquid Interfacial Reaction Trigged Propagation of Phase Transition from Surface into Bulk Lattice of Ni-Rich Layered Cathode Zou, Lianfeng; Liu, Zhenyu; Zhao, Wengao Chemistry of Materials, Vol. 30, Issue 20 https://doi.org/10.1021/acs.chemmater.8b01958	journal	September 2018
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
Accurate Determination of Coulombic Efficiency for Lithium Metal Anodes and Lithium Metal Batteries Adams, Brian D.; Zheng, Jianming; Ren, Xiaodi Advanced Energy Materials, Vol. 8, Issue 7 https://doi.org/10.1002/aenm.201702097	journal	October 2017
New Concepts in Electrolytes Li, Matthew; Wang, Chunsheng; Chen, Zhongwei Chemical Reviews https://doi.org/10.1021/acs.chemrev.9b00531	journal	February 2020

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