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Title: Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures

Abstract

In the presence of Lewis acid salts, the cyclic ether, dioxolane (DOL), is known to undergo ring-opening polymerization inside electrochemical cells to form solid-state polymer batteries with good interfacial charge-transport properties. Here we report that LiNO 3 , which is unable to ring-open DOL, possesses a previously unknown ability to coordinate with and strain DOL molecules in bulk liquids, completely arresting their crystallization. The strained DOL electrolytes exhibit physical properties analogous to amorphous polymers, including a prominent glass transition, elevated moduli, and low activation entropy for ion transport, but manifest unusually high, liquidlike ionic conductivities (e.g., 1 mS/cm) at temperatures as low as −50 °C. Systematic electrochemical studies reveal that the electrolytes also promote reversible cycling of Li metal anodes with high Coulombic efficiency (CE) on both conventional planar substrates (1 mAh/cm 2 over 1,000 cycles with 99.1% CE; 3 mAh/cm 2 over 300 cycles with 99.2% CE) and unconventional, nonplanar/three-dimensional (3D) substrates (10 mAh/cm 2 over 100 cycles with 99.3% CE). Our finding that LiNO 3 promotes reversibility of Li metal electrodes in liquid DOL electrolytes by a physical mechanism provides a possible solution to a long-standing puzzle in the field about the versatility of LiNO 3 salt additivesmore » for enhancing reversibility of Li metal electrodes in essentially any aprotic liquid electrolyte solvent. As a first step toward understanding practical benefits of these findings, we create functional Li||lithium iron phosphate (LFP) batteries in which LFP cathodes with high capacity (5 to 10 mAh/cm 2 ) are paired with thin (50 μm) lithium metal anodes, and investigate their galvanostatic electrochemical cycling behaviors.« less

Authors:
ORCiD logo; ; ; ; ORCiD logo; ; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1670470
Grant/Contract Number:  
SC0016082
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 117 Journal Issue: 42; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Zhao, Qing, Liu, Xiaotun, Zheng, Jingxu, Deng, Yue, Warren, Alexander, Zhang, Qiyuan, and Archer, Lynden. Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures. United States: N. p., 2020. Web. https://doi.org/10.1073/pnas.2004576117.
Zhao, Qing, Liu, Xiaotun, Zheng, Jingxu, Deng, Yue, Warren, Alexander, Zhang, Qiyuan, & Archer, Lynden. Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures. United States. https://doi.org/10.1073/pnas.2004576117
Zhao, Qing, Liu, Xiaotun, Zheng, Jingxu, Deng, Yue, Warren, Alexander, Zhang, Qiyuan, and Archer, Lynden. Mon . "Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures". United States. https://doi.org/10.1073/pnas.2004576117.
@article{osti_1670470,
title = {Designing electrolytes with polymerlike glass-forming properties and fast ion transport at low temperatures},
author = {Zhao, Qing and Liu, Xiaotun and Zheng, Jingxu and Deng, Yue and Warren, Alexander and Zhang, Qiyuan and Archer, Lynden},
abstractNote = {In the presence of Lewis acid salts, the cyclic ether, dioxolane (DOL), is known to undergo ring-opening polymerization inside electrochemical cells to form solid-state polymer batteries with good interfacial charge-transport properties. Here we report that LiNO 3 , which is unable to ring-open DOL, possesses a previously unknown ability to coordinate with and strain DOL molecules in bulk liquids, completely arresting their crystallization. The strained DOL electrolytes exhibit physical properties analogous to amorphous polymers, including a prominent glass transition, elevated moduli, and low activation entropy for ion transport, but manifest unusually high, liquidlike ionic conductivities (e.g., 1 mS/cm) at temperatures as low as −50 °C. Systematic electrochemical studies reveal that the electrolytes also promote reversible cycling of Li metal anodes with high Coulombic efficiency (CE) on both conventional planar substrates (1 mAh/cm 2 over 1,000 cycles with 99.1% CE; 3 mAh/cm 2 over 300 cycles with 99.2% CE) and unconventional, nonplanar/three-dimensional (3D) substrates (10 mAh/cm 2 over 100 cycles with 99.3% CE). Our finding that LiNO 3 promotes reversibility of Li metal electrodes in liquid DOL electrolytes by a physical mechanism provides a possible solution to a long-standing puzzle in the field about the versatility of LiNO 3 salt additives for enhancing reversibility of Li metal electrodes in essentially any aprotic liquid electrolyte solvent. As a first step toward understanding practical benefits of these findings, we create functional Li||lithium iron phosphate (LFP) batteries in which LFP cathodes with high capacity (5 to 10 mAh/cm 2 ) are paired with thin (50 μm) lithium metal anodes, and investigate their galvanostatic electrochemical cycling behaviors.},
doi = {10.1073/pnas.2004576117},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 42,
volume = 117,
place = {United States},
year = {2020},
month = {10}
}

Journal Article:
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https://doi.org/10.1073/pnas.2004576117

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Works referenced in this record:

High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes
journal, March 2018

  • Chen, Shuru; Zheng, Jianming; Mei, Donghai
  • Advanced Materials, Vol. 30, Issue 21
  • DOI: 10.1002/adma.201706102

On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries
journal, January 2009

  • Aurbach, Doron; Pollak, Elad; Elazari, Ran
  • Journal of The Electrochemical Society, Vol. 156, Issue 8, p. A694-A702
  • DOI: 10.1149/1.3148721

A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010


Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells
journal, July 2019

  • Kasemchainan, Jitti; Zekoll, Stefanie; Spencer Jolly, Dominic
  • Nature Materials, Vol. 18, Issue 10
  • DOI: 10.1038/s41563-019-0438-9

Physical Orphaning versus Chemical Instability: Is Dendritic Electrodeposition of Li Fatal?
journal, May 2019


Pathways for practical high-energy long-cycling lithium metal batteries
journal, February 2019


The electrochemical behavior of 1,3-dioxolane—LiClO4 solutions—II. Contaminated solutions
journal, March 1990


Thermal stability and decomposition of lithium bis(fluorosulfonyl)imide (LiFSI) salts
journal, January 2016

  • Kerner, Manfred; Plylahan, Nareerat; Scheers, Johan
  • RSC Advances, Vol. 6, Issue 28
  • DOI: 10.1039/C5RA25048J

Superconcentrated electrolytes for a high-voltage lithium-ion battery
journal, June 2016

  • Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12032

Lithium-Sulfur Battery: Evaluation of Dioxolane-Based Electrolytes
journal, January 1989

  • Peled, E.
  • Journal of The Electrochemical Society, Vol. 136, Issue 6, p. 1621-1625
  • DOI: 10.1149/1.2096981

Interactions, Structure, and Dynamics of Polymer-Tethered Nanoparticle Blends
journal, August 2016


Cold crystallization of poly(ethylene glycol)–water systems
journal, December 2007


Polymer–inorganic solid–electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions
journal, March 2019


Reviving the lithium metal anode for high-energy batteries
journal, March 2017

  • Lin, Dingchang; Liu, Yayuan; Cui, Yi
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2017.16

A multifunctional polymer electrolyte enables ultra-long cycle-life in a high-voltage lithium metal battery
journal, January 2018

  • Dong, Tiantian; Zhang, Jianjun; Xu, Gaojie
  • Energy & Environmental Science, Vol. 11, Issue 5
  • DOI: 10.1039/C7EE03365F

Rechargeable-battery chemistry based on lithium oxide growth through nitrate anion redox
journal, October 2019


Stable Artificial Solid Electrolyte Interphases for Lithium Batteries
journal, May 2017


Electrolyte Additives for Lithium Metal Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives
journal, October 2018

  • Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier
  • Angewandte Chemie International Edition, Vol. 57, Issue 46
  • DOI: 10.1002/anie.201712702

All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents
journal, October 2019


Differential scanning calorimetry (DSC) of semicrystalline polymers
journal, October 2009


A Highly Reversible Room-Temperature Sodium Metal Anode
journal, November 2015


Solid-state polymer electrolytes with in-built fast interfacial transport for secondary lithium batteries
journal, March 2019


Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Design principles for electrolytes and interfaces for stable lithium-metal batteries
journal, September 2016


Li+-conductive polymer electrolytes derived from poly(1,3-dioxolane) and polytetrahydrofuran
journal, January 1991


Revisiting TEGDME/DIOX Binary Electrolytes for Lithium/Sulfur Batteries: Importance of Solvation Ability and Additives
journal, January 2013

  • Barchasz, Céline; Leprêtre, Jean-Claude; Patoux, Sébastien
  • Journal of The Electrochemical Society, Vol. 160, Issue 3
  • DOI: 10.1149/2.022303jes

Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review
journal, July 2017


Regulating Anions in the Solvation Sheath of Lithium Ions for Stable Lithium Metal Batteries
journal, January 2019


High-Efficiency Lithium-Metal Anode Enabled by Liquefied Gas Electrolytes
journal, August 2019


Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014


Observed bands in Raman and infrared spectra of 1,3-dioxolane and their assignments
journal, January 2013


161. Spectra of acetals. Part I. The infrared and Raman spectra of 1 : 3-dioxolan
journal, January 1959

  • Barker, S. A.; Bourne, E. J.; Pinkard, R. M.
  • Journal of the Chemical Society (Resumed)
  • DOI: 10.1039/jr9590000802

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes
journal, September 2016


Upgrading traditional liquid electrolyte via in situ gelation for future lithium metal batteries
journal, October 2018


The Li-Ion Rechargeable Battery: A Perspective
journal, January 2013

  • Goodenough, John B.; Park, Kyu-Sung
  • Journal of the American Chemical Society, Vol. 135, Issue 4
  • DOI: 10.1021/ja3091438

Quasilattice Features of Concentrated Aqueous LiNO 3 Solutions
journal, January 1971

  • Irish, D. E.; Nelson, D. L.; Brooker, M. H.
  • The Journal of Chemical Physics, Vol. 54, Issue 2
  • DOI: 10.1063/1.1674892

High-capacity rechargeable batteries based on deeply cyclable lithium metal anodes
journal, May 2018

  • Shi, Qiuwei; Zhong, Yiren; Wu, Min
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 22
  • DOI: 10.1073/pnas.1803634115

Towards stable lithium-sulfur batteries: Mechanistic insights into electrolyte decomposition on lithium metal anode
journal, July 2017


Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014

  • Lu, Yingying; Tu, Zhengyuan; Archer, Lynden A.
  • Nature Materials, Vol. 13, Issue 10
  • DOI: 10.1038/nmat4041

High rate and stable cycling of lithium metal anode
journal, February 2015

  • Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7362

Enhancing electrochemical intermediate solvation through electrolyte anion selection to increase nonaqueous Li–O 2 battery capacity
journal, July 2015

  • Burke, Colin M.; Pande, Vikram; Khetan, Abhishek
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 30
  • DOI: 10.1073/pnas.1505728112