Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes

Jiaxin Zheng; Guoyu Tan; Peng Shan; Tongchao Liu; Jiangtao Hu; Yancong Feng; Luyi Yang; Mingjian Zhang; Zonghai Chen; Yuan Lin; Jun Lu; Joerg C. Neuefeind; Yang Ren; Khalil Amine; Lin Wang Wang; Kang Xu; Feng Pan

doi:10.1016/j.chempr.2018.09.004

Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes

Jiaxin Zheng, Guoyu Tan, Peng Shan, Tongchao Liu, Jiangtao Hu, Yancong Feng, Luyi Yang, Mingjian Zhang, Zonghai Chen, Yuan Lin, Jun Lu, Joerg C. Neuefeind, Yang Ren, Khalil Amine, Lin Wang Wang, Kang Xu, Feng Pan

Research output: Contribution to journal › Article › peer-review

211 Scopus citations

Abstract

Because of their non-flammable nature, low toxicity, and low production cost, aqueous Li-ion batteries (LIBs) promise very tempting alternatives to the state-of-the-art LIBs that rely on highly flammable and toxic non-aqueous electrolytes. However, the intrinsic narrow electrochemical stability window (1.23 V) of water sets an upper limit on the practical voltage and energy output. Here, we report a super-concentrated (unsaturated) LiNO₃-based aqueous electrolyte that effectively expands the aqueous stability window to 2.55 V. We further revealed that a unique local structure with (Li⁺(H₂O)₂)_n polymer-like aggregation arises at the super-concentration, which assists in stabilizing the aqueous solution at extreme potentials via both thermodynamic and kinetic contributions. This fundamental revelation of liquid structure and its effect on the electrochemical stability window provides a new pathway for designing high-voltage aqueous electrolytes.

Original language	English
Pages (from-to)	2872-2882
Number of pages	11
Journal	Chem
Volume	4
Issue number	12
DOIs	https://doi.org/10.1016/j.chempr.2018.09.004
State	Published - Dec 13 2018
Externally published	Yes

Funding

This work was financially supported by the National Materials Genome Project (2016YFB0700600), the National Natural Science Foundation of China (21603007 and 51672012), and Shenzhen Science and Technology Research Grants (JCYJ20150729111733470 and JCYJ20151015162256516). L.-W.W. was supported by the Assistant Secretary for Energy Efficiency and Renewal Energy under the Battery Material Research program. J.L., Z.C., and K.A. gratefully acknowledge support from the Vehicle Technologies Office of the US Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy. Argonne National Laboratory is operated for the DOE Office of Science by UChicago Argonne LLC under contract no. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The neutron scattering experiments were carried out at the Spallation Neutron Source, which is sponsored by the Scientific User Facilities Division of the DOE Office of Basic Energy Sciences under contract no. DE-AC05-00OR22725 with the Oak Ridge National Laboratory. This work was financially supported by the National Materials Genome Project ( 2016YFB0700600 ), the National Natural Science Foundation of China ( 21603007 and 51672012 ), and Shenzhen Science and Technology Research Grants ( JCYJ20150729111733470 and JCYJ20151015162256516 ). L.-W.W. was supported by the Assistant Secretary for Energy Efficiency and Renewal Energy under the Battery Material Research program . J.L., Z.C., and K.A. gratefully acknowledge support from the Vehicle Technologies Office of the US Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy . Argonne National Laboratory is operated for the DOE Office of Science by UChicago Argonne LLC under contract no. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. The neutron scattering experiments were carried out at the Spallation Neutron Source, which is sponsored by the Scientific User Facilities Division of the DOE Office of Basic Energy Sciences under contract no. DE-AC05-00OR22725 with the Oak Ridge National Laboratory.

Funders	Funder number
DOE Office of Basic Energy Sciences
DOE Office of Science
Shenzhen Science and Technology Research Grants	JCYJ20151015162256516, JCYJ20150729111733470
UChicago Argonne LLC
US Department of Energy
U.S. Department of Energy
Office of Science
Office of Energy Efficiency and Renewable Energy
Argonne National Laboratory
Vehicle Technologies Office
National Natural Science Foundation of China	21603007, 51672012
National Materials Genome Project	2016YFB0700600

Keywords

LiNO aqueous solution
SDG7: Affordable and clean energy
aqueous electrolyte
electrochemical stability window
molecular dynamics simulation
pair-distribution function
polymer-like chains
super-concentrated

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.chempr.2018.09.004

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title = "Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes",

abstract = "Because of their non-flammable nature, low toxicity, and low production cost, aqueous Li-ion batteries (LIBs) promise very tempting alternatives to the state-of-the-art LIBs that rely on highly flammable and toxic non-aqueous electrolytes. However, the intrinsic narrow electrochemical stability window (1.23 V) of water sets an upper limit on the practical voltage and energy output. Here, we report a super-concentrated (unsaturated) LiNO3-based aqueous electrolyte that effectively expands the aqueous stability window to 2.55 V. We further revealed that a unique local structure with (Li+(H2O)2)n polymer-like aggregation arises at the super-concentration, which assists in stabilizing the aqueous solution at extreme potentials via both thermodynamic and kinetic contributions. This fundamental revelation of liquid structure and its effect on the electrochemical stability window provides a new pathway for designing high-voltage aqueous electrolytes.",

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author = "Jiaxin Zheng and Guoyu Tan and Peng Shan and Tongchao Liu and Jiangtao Hu and Yancong Feng and Luyi Yang and Mingjian Zhang and Zonghai Chen and Yuan Lin and Jun Lu and Neuefeind, {Joerg C.} and Yang Ren and Khalil Amine and Wang, {Lin Wang} and Kang Xu and Feng Pan",

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doi = "10.1016/j.chempr.2018.09.004",

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AU - Zheng, Jiaxin

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AU - Hu, Jiangtao

AU - Feng, Yancong

AU - Yang, Luyi

AU - Zhang, Mingjian

AU - Chen, Zonghai

AU - Lin, Yuan

AU - Lu, Jun

AU - Neuefeind, Joerg C.

AU - Ren, Yang

AU - Amine, Khalil

AU - Wang, Lin Wang

AU - Xu, Kang

AU - Pan, Feng

PY - 2018/12/13

Y1 - 2018/12/13

N2 - Because of their non-flammable nature, low toxicity, and low production cost, aqueous Li-ion batteries (LIBs) promise very tempting alternatives to the state-of-the-art LIBs that rely on highly flammable and toxic non-aqueous electrolytes. However, the intrinsic narrow electrochemical stability window (1.23 V) of water sets an upper limit on the practical voltage and energy output. Here, we report a super-concentrated (unsaturated) LiNO3-based aqueous electrolyte that effectively expands the aqueous stability window to 2.55 V. We further revealed that a unique local structure with (Li+(H2O)2)n polymer-like aggregation arises at the super-concentration, which assists in stabilizing the aqueous solution at extreme potentials via both thermodynamic and kinetic contributions. This fundamental revelation of liquid structure and its effect on the electrochemical stability window provides a new pathway for designing high-voltage aqueous electrolytes.

AB - Because of their non-flammable nature, low toxicity, and low production cost, aqueous Li-ion batteries (LIBs) promise very tempting alternatives to the state-of-the-art LIBs that rely on highly flammable and toxic non-aqueous electrolytes. However, the intrinsic narrow electrochemical stability window (1.23 V) of water sets an upper limit on the practical voltage and energy output. Here, we report a super-concentrated (unsaturated) LiNO3-based aqueous electrolyte that effectively expands the aqueous stability window to 2.55 V. We further revealed that a unique local structure with (Li+(H2O)2)n polymer-like aggregation arises at the super-concentration, which assists in stabilizing the aqueous solution at extreme potentials via both thermodynamic and kinetic contributions. This fundamental revelation of liquid structure and its effect on the electrochemical stability window provides a new pathway for designing high-voltage aqueous electrolytes.

KW - LiNO aqueous solution

KW - SDG7: Affordable and clean energy

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KW - electrochemical stability window

KW - molecular dynamics simulation

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Understanding Thermodynamic and Kinetic Contributions in Expanding the Stability Window of Aqueous Electrolytes

Abstract

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Keywords

UN SDGs

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