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Room Temperature to 150 °C Lithium Metal Batteries Enabled by a Rigid Molecular Ionic Composite Electrolyte

Journal Article · · Advanced Energy Materials

Molecular ionic composites (MICs), made from ionic liquids and a rigid-rod polymer poly(2,2'-disulfonyl-4,4'-benzidine terephthalamide) (PBDT), are a new type of rigid gel electrolyte that combine fast ion transport with high thermal stability and mechanical strength. In this work, a MIC electrolyte membrane is prepared that is composed of PBDT, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr14TFSI) in a mass ratio of 10:10:80. The ionic conductivity at 25 °C is 0.56 mS cm–1 with no added flammable/volatile components. Although the polymer content is only 10 wt%, this MIC membrane is rigid with a tensile modulus of 410 MPa at room temperature. The MIC membrane remains stable and rigid at 200 °C with the shear storage modulus (G') only slightly decreasing by 35%. Li/MIC/LiFePO4 cells demonstrate stable cycling performance over a wide temperature range from 23 to 150 °C. The specific discharge capacity at 100 and 150 °C at 1 C rate exceeds 160 mAh g–1. The discharge capacity retention is 99% after 50 cycles at 150 °C. Furthermore, this stable battery performance shows that this low polymer content MIC membrane qualifies for use as a solid electrolyte in lithium metal batteries operating over a wide temperature range.

Research Organization:
Virginia Polytechnic Institute and State University (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
EE0008860
OSTI ID:
2006596
Alternate ID(s):
OSTI ID: 1804513
OSTI ID: 1848917
OSTI ID: 23098880
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 12 Vol. 11; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (72)

Rigid rod water-soluble polymers journal October 1996
Highly Conductive and Thermally Stable Ion Gels with Tunable Anisotropy and Modulus journal January 2016
Self-Healing Micellar Ion Gels Based on Multiple Hydrogen Bonding journal July 2018
New Insights to Self-Aggregation in Ionic Liquid Electrolytes for High-Energy Electrochemical Devices journal February 2011
A Composite Gel Polymer Electrolyte with High Performance Based on Poly(Vinylidene Fluoride) and Polyborate for Lithium Ion Batteries journal August 2013
Hexagonal Boron Nitride-Based Electrolyte Composite for Li-Ion Battery Operation from Room Temperature to 150 °C journal April 2016
Crosslinked Poly(tetrahydrofuran) as a Loosely Coordinating Polymer Electrolyte journal July 2018
Decoupling the Ionic Conductivity and Elastic Modulus of Gel Electrolytes: Fully Zwitterionic Copolymer Scaffolds in Lithium Salt/Ionic Liquid Solutions journal July 2018
Oxygen Release Degradation in Li‐Ion Battery Cathode Materials: Mechanisms and Mitigating Approaches journal April 2019
In Situ Synthesis of Imidazolium-Crosslinked Ionogels via Debus-Radziszewski Reaction Based on PAMAM Dendrimers in Imidazolium Ionic liquid journal September 2017
Synthesis and properties of methacrylate-based networked polymers having ionic liquid structures journal September 2010
Broadband Dielectric Spectroscopy book January 2003
Rheological properties and impedance spectroscopy of PMMA-PVdF blend and PMMA gel polymer electrolytes for advanced lithium batteries journal January 2005
Electrochemical measurement of transference numbers in polymer electrolytes journal December 1987
A high-temperature lithiumcopper oxide cell with a solid polymer electrolyte journal October 1991
Review of gel-type polymer electrolytes for lithium-ion batteries journal February 1999
Trends in polymer electrolytes for secondary lithium batteries journal June 2000
Review on high temperature secondary Li-ion batteries journal October 2018
Development and implementation of a high temperature electrochemical cell for lithium batteries journal April 2007
Dendrite short-circuit and fuse effect on Li/polymer/Li cells journal July 2006
Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study journal April 2011
Polymer electrolytes—Some principles, cautions, and new practices journal October 2017
In-situ plasticized polymer electrolyte with double-network for flexible solid-state lithium-metal batteries journal January 2018
Graft copolymer-based lithium-ion battery for high-temperature operation journal July 2011
Characterization of N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide-based polymer electrolytes for high safety lithium batteries journal February 2013
A novel polymer electrolyte with improved high-temperature-tolerance up to 170 °C for high-temperature lithium-ion batteries journal December 2013
Lithium secondary batteries working at very high temperature: Capacity fade and understanding of aging mechanisms journal August 2013
High-performance N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide/poly(vinylidene fluoride-hexafluoropropylene) gel polymer electrolytes for lithium metal batteries journal November 2018
Water and sodium transport and liquid crystalline alignment in a sulfonated aramid membrane journal September 2015
Mechanically strong ionogels formed by immobilizing ionic liquid in polyzwitterion networks journal December 2017
Dynamic mechanical properties of gel polymer electrolytes containing ionic liquid journal October 2008
Enhanced working temperature of PEO-based polymer electrolyte via porous PTFE film as an efficient heat resister journal September 2013
High-Performance Double-Network Ion Gels with Fast Thermal Healing Capability via Dynamic Covalent Bonds journal October 2018
Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review journal July 2017
Molecular Structure and Dynamics of Ionic Liquids in a Rigid-Rod Polyanion-Based Ion Gel journal December 2016
Sulfonated Polyimide/Ionic Liquid Composite Membranes for CO 2 Separation: Transport Properties in Relation to Their Nanostructures journal September 2018
Ion Transport and Mechanical Properties of Non-Crystallizable Molecular Ionic Composite Electrolytes journal February 2020
Gel Electrolyte Comprising Solvate Ionic Liquid and Methyl Cellulose journal December 2019
Quasi-Solid Electrolytes for High Temperature Lithium Ion Batteries journal November 2015
High Conductivity, High Strength Solid Electrolytes Formed by in Situ Encapsulation of Ionic Liquids in Nanofibrillar Methyl Cellulose Networks journal May 2016
Nanofibrillar Ionic Polymer Composites Enable High-Modulus Ion-Conducting Membranes journal September 2019
Application of Protic Ionic Liquids to CO 2 Separation in a Sulfonated Polyimide-Derived Ion Gel Membrane journal May 2019
Challenges for Rechargeable Li Batteries journal February 2010
Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries journal October 2004
Nonhumidified Intermediate Temperature Fuel Cells Using Protic Ionic Liquids journal July 2010
Physicochemical Properties and Structures of Room-Temperature Ionic Liquids. 3. Variation of Cationic Structures journal February 2006
Pyrrolidinium Imides:  A New Family of Molten Salts and Conductive Plastic Crystal Phases journal May 1999
High Ionic Liquid Content Polymeric Gel Membranes: Preparation and Performance journal January 2011
Molecular Alignment and Ion Transport in Rigid Rod Polyelectrolyte Solutions journal April 2014
Highly Efficient and Specific Gelation of Ionic Liquids by Polymeric Electrolytes to Form Ionogels with Substantially High Gel–Sol Transition Temperatures and Rheological Properties Like Self-Standing Ability and Rapid Recovery journal August 2012
Issues and challenges facing rechargeable lithium batteries journal November 2001
Sulfonated polyimide/ionic liquid composite membranes for carbon dioxide separation journal June 2017
Double helical conformation and extreme rigidity in a rodlike polyelectrolyte journal February 2019
Taichi-inspired rigid-flexible coupling cellulose-supported solid polymer electrolyte for high-performance lithium batteries journal September 2014
Lithium metal anodes for rechargeable batteries journal January 2014
Hybrid ionogel electrolytes for high temperature lithium batteries journal January 2015
High temperature electrical energy storage: advances, challenges, and frontiers journal January 2016
Transition of lithium growth mechanisms in liquid electrolytes journal January 2016
Polymer electrolytes for lithium polymer batteries journal January 2016
Design criteria for electrochemical shock resistant battery electrodes journal January 2012
Spin Diffusion Measurements: Spin Echoes in the Presence of a Time‐Dependent Field Gradient journal January 1965
Materials for lithium-ion battery safety journal June 2018
MATERIALS SCIENCE: A Unique Platform for Materials Design journal July 2008
Chemical Expansion: Implications for Electrochemical Energy Storage and Conversion Devices journal July 2014
High Lithium Metal Cycling Efficiency in a Room-Temperature Ionic Liquid journal January 2004
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries journal April 1997
Characterization of the Lithium Surface in N-Methyl-N-alkylpyrrolidinium Bis(trifluoromethanesulfonyl)amide Room-Temperature Ionic Liquid Electrolytes journal January 2006
The Development and Future of Lithium Ion Batteries journal December 2016
Comparing Cycling Characteristics of Symmetric Lithium-Polymer-Lithium Cells with Theoretical Predictions journal January 2018
Electrochemistry at Negative Potentials in Bis(trifluoromethanesulfonyl)amide Ionic Liquids journal October 2006
Ionic Liquid-Based Electrolyte Membranes for Medium-High Temperature Lithium Polymer Batteries journal July 2018
Role of Cation Structure in CO2 Separation by Ionic Liquid/Sulfonated Polyimide Composite Membrane journal July 2019

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