Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Sub-nanometer confinement enables facile condensation of gas electrolyte for low-temperature batteries

Journal Article · · Nature Communications

Abstract

Confining molecules in the nanoscale environment can lead to dramatic changes of their physical and chemical properties, which opens possibilities for new applications. There is a growing interest in liquefied gas electrolytes for electrochemical devices operating at low temperatures due to their low melting point. However, their high vapor pressure still poses potential safety concerns for practical usages. Herein, we report facile capillary condensation of gas electrolyte by strong confinement in sub-nanometer pores of metal-organic framework (MOF). By designing MOF-polymer membranes (MPMs) that present dense and continuous micropore (~0.8 nm) networks, we show significant uptake of hydrofluorocarbon molecules in MOF pores at pressure lower than the bulk counterpart. This unique property enables lithium/fluorinated graphite batteries with MPM-based electrolytes to deliver a significantly higher capacity than those with commercial separator membranes (~500 mAh g −1 vs. <0.03 mAh g −1 ) at −40 °C under reduced pressure of the electrolyte.

Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1786834
Alternate ID(s):
OSTI ID: 1816300
Journal Information:
Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 12; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United Kingdom
Language:
English

References (60)

A Metal-Organic-Framework-Based Electrolyte with Nanowetted Interfaces for High-Energy-Density Solid-State Lithium Battery journal November 2017
A Metal Organic Framework Derived Solid Electrolyte for Lithium–Sulfur Batteries journal June 2020
Designing Advanced Lithium‐Based Batteries for Low‐Temperature Conditions journal August 2020
High‐Energy Rechargeable Metallic Lithium Battery at −70 °C Enabled by a Cosolvent Electrolyte journal March 2019
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
Thin-film electrochemical sensor electrode for rapid evaluation of electrolytic conductivity, cyclic voltammetry, and temperature measurements journal June 2015
Methane adsorption on microporous carbons—A comparison of experiment, theory, and simulation journal January 1992
The LiSOCl2 cell — a review journal November 1988
A comprehensive review of lithium-ion batteries used in hybrid and electric vehicles at cold temperatures journal February 2016
Porous Metal-Organic Frameworks: Promising Materials for Methane Storage journal October 2016
Capillary condensation of adsorbates in porous materials journal November 2011
Heating strategies for Li-ion batteries operated from subzero temperatures journal September 2013
The use of lithium-ion batteries for JPL's Mars missions journal April 2018
A review on capillary condensation in nanoporous media: Implications for hydrocarbon recovery from tight reservoirs journal November 2016
The Kelvin equation journal January 2008
Metal-Organic Frameworks for Batteries journal November 2018
A Metal-Organic Framework Host for Highly Reversible Dendrite-free Zinc Metal Anodes journal May 2019
High-Efficiency Lithium-Metal Anode Enabled by Liquefied Gas Electrolytes journal August 2019
Nanopore confinement effects on phase behavior and capillary pressure in a Wolfcamp shale reservoir journal September 2017
Effect of Benzoic Acid as a Modulator in the Structure of UiO-66: An Experimental and Computational Study journal April 2017
Li + -Desolvation Dictating Lithium-Ion Battery’s Low-Temperature Performances journal November 2017
Synthesis and Stability of Tagged UiO-66 Zr-MOFs journal December 2010
High Pressure Adsorption of CO 2 and CH 4 on Zr-MOFs journal April 2014
A Solid Lithium Electrolyte via Addition of Lithium Isopropoxide to a Metal–Organic Framework with Open Metal Sites journal September 2011
Water Adsorption in Porous Metal–Organic Frameworks and Related Materials journal March 2014
A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability
  • Cavka, Jasmina Hafizovic; Jakobsen, Søren; Olsbye, Unni
  • Journal of the American Chemical Society, Vol. 130, Issue 42, p. 13850-13851 https://doi.org/10.1021/ja8057953
journal October 2008
Single-Ion Li + , Na + , and Mg 2+ Solid Electrolytes Supported by a Mesoporous Anionic Cu–Azolate Metal–Organic Framework journal September 2017
Tuning the Adsorption Properties of UiO-66 via Ligand Functionalization journal October 2012
Graphene Oxide Papers Modified by Divalent Ions—Enhancing Mechanical Properties via Chemical Cross-Linking journal March 2008
Direct experimental verification of the Kelvin equation for capillary condensation journal February 1979
Lithium-ion battery structure that self-heats at low temperatures journal January 2016
Metal–organic framework-based separator for lithium–sulfur batteries journal June 2016
A materials perspective on Li-ion batteries at extreme temperatures journal July 2017
3D microstructure design of lithium-ion battery electrodes assisted by X-ray nano-computed tomography and modelling journal April 2020
All-temperature batteries enabled by fluorinated electrolytes with non-polar solvents journal October 2019
Chemical reactivity under nanoconfinement journal April 2020
Thermodynamics of liquids: standard molar entropies and heat capacities of common solvents from 2PT molecular dynamics journal January 2011
Metal–Organic Frameworks (MOFs) journal January 2014
Carbon dioxide in the cage: manganese metal–organic frameworks for high performance CO 2 electrodes in Li–CO 2 batteries journal January 2018
An ester electrolyte for lithium–sulfur batteries capable of ultra-low temperature cycling journal January 2020
Liquefied gas electrolytes for wide-temperature lithium metal batteries journal January 2020
The two-phase model for calculating thermodynamic properties of liquids from molecular dynamics: Validation for the phase diagram of Lennard-Jones fluids journal December 2003
Polymorphic transitions in single crystals: A new molecular dynamics method journal December 1981
Constant pressure molecular dynamics algorithms journal September 1994
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal September 2014
MCCCS Towhee: a tool for Monte Carlo molecular simulation journal December 2013
A Liouville-operator derived measure-preserving integrator for molecular dynamics simulations in the isothermal–isobaric ensemble journal April 2006
Encapsulating soluble active species into hollow crystalline porous capsules beyond integration of homogeneous and heterogeneous catalysis journal October 2019
Computer Simulation of Liquids book June 2017
Rapid estimation of elastic constants by molecular dynamics simulation under constant stress journal April 2004
Energy Storage Technologies for Small Satellite Applications journal March 2018
The Chemistry and Applications of Metal-Organic Frameworks journal August 2013
Metal-organic framework nanosheets as building blocks for molecular sieving membranes journal December 2014
A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n journal February 1999
Synthetic nacre by predesigned matrix-directed mineralization journal August 2016
Liquefied gas electrolytes for electrochemical energy storage devices journal June 2017
Impact-resistant nacre-like transparent materials journal June 2019
Balancing volumetric and gravimetric uptake in highly porous materials for clean energy journal April 2020
Discharge Reaction Mechanisms in Li / SOCl2 Cells journal April 1979
Sulfuryl and Thionyl Halide-Based Ultralow Temperature Primary Batteries journal January 2010

Similar Records

Electronic tuning of confined sub-nanometer cobalt oxide clusters boosting oxygen catalysis and rechargeable Zn–air batteries.
Journal Article · Sat May 01 00:00:00 EDT 2021 · Nano Energy · OSTI ID:1813126

Characterization of a Molecule Partially Confined at the Pore Mouth of a Zeotype
Journal Article · Thu Mar 18 00:00:00 EDT 2021 · Angewandte Chemie · OSTI ID:1786035

Related Subjects