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Title: Crosslinked Poly(tetrahydrofuran) as a Loosely Coordinating Polymer Electrolyte

Journal Article · · Advanced Energy Materials
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Stanford University Department of Chemical Engineering Shriram Center 443 Via Ortega, Room 307 Stanford CA 94305‐4125 USA
  2. Stanford University Department of Materials Science McCullough 476 Lomita Mall, Room 343 Stanford CA 94305 USA

Abstract Solid polymer electrolytes (SPEs) promise to improve the safety and performance of lithium ion batteries (LIBs). However, the low ionic conductivity and transference number of conventional poly(ethylene oxide) (PEO)‐based SPEs preclude their widespread implementation. Herein, crosslinked poly(tetrahydrofuran) (xPTHF) is introduced as a promising polymer matrix for “beyond PEO” SPEs. The crosslinking procedure creates thermally stable, mechanically robust membranes for use in LIBs. Molecular dynamics and density functional theory (DFT) simulations accompanied by 7 Li NMR measurements show that the lower spatial concentration of oxygen atoms in the xPTHF backbone leads to loosened O–Li + coordination. This weakened interaction enhances ion transport; xPTHF has a high lithium transference number of 0.53 and higher lithium conductivity than a xPEO SPE of the same length at room temperature. It is demonstrated that organic additives further weaken the O–Li + interaction, enabling room temperature ionic conductivity of 1.2 × 10 −4 S cm −1 with 18 wt% N,N ‐dimethylformamide in xPTHF. In a solid‐state LIB application, neat xPTHF SPEs cycle with near theoretical capacity for 100 cycles at 70 °C, with rate capability up to 1 C. The plasticized xPTHF SPEs operate at room temperature while maintaining respectable rate capability and capacity. The novel PTHF system demonstrated here represents an exciting platform for future studies involving SPEs.

Sponsoring Organization:
USDOE
OSTI ID:
1460461
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Vol. 8 Journal Issue: 25; ISSN 1614-6832
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English
Citation Metrics:
Cited by: 152 works
Citation information provided by
Web of Science

References (86)

Transferable Potentials for Phase Equilibria. 6. United-Atom Description for Ethers, Glycols, Ketones, and Aldehydes journal November 2004
The plastic-crystalline phase of succinonitrile as a universal matrix for solid-state ionic conductors journal June 2004
Preparation of organic/inorganic hybrid semi-interpenetrating network polymer electrolytes based on poly(ethylene oxide-co-ethylene carbonate) for all-solid-state lithium batteries at elevated temperatures journal June 2014
Electrochemical comparison of several cross-linked polyethers journal April 1998
Correlation between Solvation Structure and Ion-Conductive Behavior of Concentrated Poly(ethylene carbonate)-Based Electrolytes journal June 2016
Issues and challenges facing rechargeable lithium batteries journal November 2001
Conductivities, thermal properties and Raman studies of poly(tetramethylene glycol) based polymer electrolytes journal April 1998
Single-Ion Conducting Polymer Electrolytes for Lithium Metal Polymer Batteries that Operate at Ambient Temperature journal September 2016
A Superior Polymer Electrolyte with Rigid Cyclic Carbonate Backbone for Rechargeable Lithium Ion Batteries journal May 2017
Poly(ethylene oxide)-based electrolytes for lithium-ion batteries journal January 2015
Polymer solid electrolytes based on viologen-type poly(oxytetramethylene) ionene journal April 2004
In Situ Generation of Poly (Vinylene Carbonate) Based Solid Electrolyte with Interfacial Stability for LiCoO 2 Lithium Batteries journal November 2016
Effect of donor number of solvent on the conductivity behaviour of nonaqueous proton-conducting polymer gel electrolytes journal June 2003
Solid Hybrid Polymer Electrolyte Networks: Nano-Structurable Materials for Lithium Batteries journal August 2002
Cross-Linked Solid Polymer Electrolyte for All-Solid-State Rechargeable Lithium Batteries journal December 2016
High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis journal August 2017
Variation of the mesh size of PEO-based networks filled with TFSILi: from an Arrhenius to WLF type conductivity behavior journal February 2000
Interfacial Challenges in Solid-State Li Ion Batteries journal October 2015
Flexible Organic–Inorganic Hybrid Solid Electrolytes Formed via Thiol–Acrylate Photopolymerization journal February 2017
Polymer Electrolytes journal July 2013
Fast Li-ion conduction in poly(ethylene carbonate)-based electrolytes and composites filled with TiO 2 nanoparticles journal January 2014
GROMACS: High performance molecular simulations through multi-level parallelism from laptops to supercomputers journal September 2015
Ionic conductivity in crystalline polymer electrolytes journal August 2001
Review of gel-type polymer electrolytes for lithium-ion batteries journal February 1999
Li+-conductive polymer electrolytes derived from poly(1,3-dioxolane) and polytetrahydrofuran journal January 1991
In situ preparation of poly(ethylene oxide)–SiO2 composite polymer electrolytes journal April 2004
Systematic Computational and Experimental Investigation of Lithium-Ion Transport Mechanisms in Polyester-Based Polymer Electrolytes journal July 2015
7 Li NMR chemical shift titration and theoretical DFT calculation studies: solvent and anion effects on second-order complexation of 12-crown-4 and 1-aza-12-crown-4 with Lithium cation in several aprotic solvents: 7 Li NMR shift titration: solvent and anion studies on 12-crown-4 and 1-aza-12-crown-4 journal November 2009
CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields journal January 2009
Complexes of alkali metal ions with poly(ethylene oxide) journal November 1973
Polymer electrolytes for lithium polymer batteries journal January 2016
Effect of propylene carbonate as a plasticizer in high molecular weight PEO_LiCF3SO3 electrolytes journal May 1996
Vibrational, ac impedance and dielectric spectroscopic studies of poly(vinylacetate)–N,N–dimethylformamide–LiClO4 polymer gel electrolytes journal August 2004
A comparison of models for calculating nuclear magnetic resonance shielding tensors journal April 1996
Lithium ion conductivity in polyoxyethylene/polyethylenimine blends journal March 2001
Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes journal March 1998
Review—Solid Electrolytes in Rechargeable Electrochemical Cells journal January 2015
Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts journal March 2006
Replies to comments contained in “Conductivity hysteresis in polymer electrolytes incorporating poly(tetrahydrofuran)” by O. Akbulut, et al., Electrochim. Acta 52 (2007) 1983 journal August 2007
Conductivity hysteresis in polymer electrolytes incorporating poly(tetrahydrofuran) journal January 2007
What Can We Learn from Ionic Conductivity Measurements in Polymer Electrolytes? A Case Study on Poly(ethylene oxide) (PEO)–NaI and PEO–LiTFSI journal February 2012
Review—On Order and Disorder in Polymer Electrolytes journal January 2015
Brønsted acid-free controlled polymerization of tetrahydrofuran catalyzed by recyclable rare earth triflates in the presence of epoxides journal August 2012
The effects of radiation-induced crosslinking on the conductance of LiClO4·PEO electrolytes journal January 1984
The Compensation Effect in the Vogel–Tammann–Fulcher (VTF) Equation for Polymer-Based Electrolytes journal May 2017
Thermal stability and decomposition of lithium bis(fluorosulfonyl)imide (LiFSI) salts journal January 2016
Computational Investigation on the Role of Plasticizers on Ion Conductivity in Poly(ethylene oxide) LiTFSI Electrolytes journal April 2010
Nonflammable perfluoropolyether-based electrolytes for lithium batteries journal February 2014
Super Soft All-Ethylene Oxide Polymer Electrolyte for Safe All-Solid Lithium Batteries journal January 2016
Improved Description of Nuclear Magnetic Resonance Chemical Shielding Constants Using the M06-L Meta-Generalized-Gradient-Approximation Density Functional journal July 2008
Ionic Conductivity of Polymeric Solid Electrolytes Based on Poly(propylene oxide) or Poly(tetramethylene oxide) journal November 1982
Improvement of heat stability of poly(l-lactic acid) by radiation-induced crosslinking journal June 2005
Thermally cured semi-interpenetrating electrolyte networks (s-IPN) for safe and aging-resistant secondary lithium polymer batteries journal February 2016
Measurement of transference numbers for lithium ion electrolytes via four different methods, a comparative study journal April 2011
Fire retardant, superionic solid state polymer electrolyte membranes for lithium ion batteries journal February 2017
Nanocomposite polymer electrolytes for lithium batteries journal July 1998
Highly conductive, completely amorphous polymer electrolyte membranes fabricated through photo-polymerization of poly(ethylene glycol diacrylate) in mixtures of solid plasticizer and lithium salt journal January 2014
A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions journal November 2006
Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks journal August 2017
Suppression of Lithium Dendrite Growth Using Cross-Linked Polyethylene/Poly(ethylene oxide) Electrolytes: A New Approach for Practical Lithium-Metal Polymer Batteries journal May 2014
Thermal, electrical and mechanical properties of plasticized polymer electrolytes based on PEO/P(VDF-HFP) blends journal November 2002
Electrochemical measurement of transference numbers in polymer electrolytes journal December 1987
Investigation on solvent-free solid polymer electrolytes for advanced lithium batteries and their performance journal February 2003
Performance of gel-type polymer electrolytes according to the affinity between polymer matrix and plasticizing solvent molecules journal February 2001
Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes journal January 2017
NMR determination of ionic structure in plasticized polyether-urethane polymer electrolytes journal May 1996
Polymer electrolytes journal January 1993
In-situ plasticized polymer electrolyte with double-network for flexible solid-state lithium-metal batteries journal January 2018
Crystal Structure of the Polymer Electrolyte Poly(ethylene oxide)3:LiCF3SO3 journal November 1993
Solid polymer electrolytes: materials designing and all-solid-state battery applications: an overview journal October 2008
Importance of donor number in determining solvating ability of polymers and transport properties in gel-type polymer electrolytes journal March 2000
PEO-Based Electrolyte Membranes Based on LiBC[sub 4]O[sub 8] Salt journal January 2004
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets journal April 1984
Photocured PEO-based solid polymer electrolyte and its application to lithium–polymer batteries journal January 2001
Mechanism of ion transport in PEO/LiTFSI complexes: Effect of temperature, molecular weight and end groups journal October 2012
Electrochemical characterization of new conducting polymer electrolytes journal June 1993
Hybrid Electrolytes with Controlled Network Structures for Lithium Metal Batteries journal August 2015
Monte Carlo Calculations for Alcohols and Their Mixtures with Alkanes. Transferable Potentials for Phase Equilibria. 5. United-Atom Description of Primary, Secondary, and Tertiary Alcohols journal April 2001
A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles journal December 2015
Phase Behavior and Electrochemical Characterization of Blends of Perfluoropolyether, Poly(ethylene glycol), and a Lithium Salt journal January 2015
Structure and Ionic Conductivity of Polystyrene- block -poly(ethylene oxide) Electrolytes in the High Salt Concentration Limit journal February 2016
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction journal December 2015
A perspective on nickel-rich layered oxide cathodes for lithium-ion batteries journal January 2017
Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions journal October 2004
Ionic conductivity, glass transition, and local free volume in poly(ethylene oxide) electrolytes: Single and mixed ion conductors journal May 2003
High rate and stable cycling of lithium metal anode journal February 2015