Effect of network homogeneity on mechanical, thermal and electrochemical properties of solid polymer electrolytes prepared by homogeneous 4-arm poly(ethylene glycols).

Mechanically tough solid polymer electrolytes (SPEs) are required to meet the demand for flexible and stretchable electrochemical devices for diverse applications, especially for wearable devices. It is well known that the inhomogeneity of a polymer network greatly affects its mechanical properties, but the evaluation of its effect on electrolyte properties including mechanical properties has not been accomplished yet because of the coexistence of various inhomogeneities (e.g., dangling bonds, loops, chain entanglements, and inhomogeneous distribution of cross-linking points). Herein, we discuss the effect of distribution of cross-linking densities in SPEs on its electrolyte properties by employing a model polymer network composed of a homogeneous 4-arm poly(ethylene glycol) (tetra-PEG) network and Li[TFSA] ([TFSA]: bis(trifluoromethanesulfonyl)amide). Tetra-PEGs having different molecular weights (Mn = 5, 10, 20, and 40 kDa) are subjected to the Michael addition reaction to induce network inhomogeneity while the average cross-linking densities are matched. It was found that thermal and ion transport properties of tetra-PEG SPEs do not depend on network inhomogeneity but on the average network size, which indicates that these properties reflect the averaged thermal fluctuation of polymer chains in terms of spatial and temporal dimensions. On the other hand, the mechanical toughness was largely dependent on the network homogeneity, and fracture strain, energy, and Young's modulus decreased by introducing network inhomogeneity. Rheological measurements showed that a transient cross-linking between Li cations and oxygens of tetra-PEG as well as the homogeneous distribution of the chemical cross-linking points contribute to the excellent mechanical properties of SPEs.

[1]  M. Shibayama,et al.  Polymer gel with a flexible and highly ordered three-dimensional network synthesized via bond percolation , 2019, Science Advances.

[2]  Xiaokun Zhang,et al.  Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries , 2019, Nature Nanotechnology.

[3]  M. Watanabe,et al.  Polymer electrolytes based on a homogeneous poly(ethylene glycol) network and their application to polymer actuators , 2019, Electrochimica Acta.

[4]  Jeong Sook Ha,et al.  Stretchable, Skin-Attachable Electronics with Integrated Energy Storage Devices for Biosignal Monitoring. , 2019, Accounts of chemical research.

[5]  Yan Yu,et al.  Progress of enhancing the safety of lithium ion battery from the electrolyte aspect , 2019, Nano Energy.

[6]  Xiangsong Lin,et al.  Effects of Cross-Link Density and Distribution on Static and Dynamic Properties of Chemically Cross-Linked Polymers , 2019, Macromolecules.

[7]  Chenhui Zhu,et al.  Phase Behavior of Mixtures of Block Copolymers and a Lithium Salt. , 2018, The journal of physical chemistry. B.

[8]  Jonas Mindemark,et al.  Beyond PEO—Alternative host materials for Li + -conducting solid polymer electrolytes , 2018, Progress in Polymer Science.

[9]  Qi Li,et al.  Recent Progress of the Solid‐State Electrolytes for High‐Energy Metal‐Based Batteries , 2018 .

[10]  T. Kyu,et al.  Effect of dangling side branching of polymer electrolyte membrane at the electrode interface on enhancement of ionic conductivity and capacity retention , 2018 .

[11]  Wei Luo,et al.  Promises, Challenges, and Recent Progress of Inorganic Solid‐State Electrolytes for All‐Solid‐State Lithium Batteries , 2018, Advanced materials.

[12]  Yutao Li,et al.  PEO/garnet composite electrolytes for solid-state lithium batteries: From “ceramic-in-polymer” to “polymer-in-ceramic” , 2017 .

[13]  Rui Zhang,et al.  An anion-immobilized composite electrolyte for dendrite-free lithium metal anodes , 2017, Proceedings of the National Academy of Sciences.

[14]  Hong‐Jie Peng,et al.  A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries. , 2017, Chemical Society reviews.

[15]  Rui Zhang,et al.  Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. , 2017, Chemical reviews.

[16]  Jyotirmoy Mandal,et al.  A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries. , 2017, Nano letters.

[17]  M. Watanabe,et al.  Tetra-PEG Network Containing Ionic Liquid Synthesized via Michael Addition Reaction and Its Application to Polymer Actuator , 2017 .

[18]  David P. Wilkinson,et al.  Recent advances in all-solid-state rechargeable lithium batteries , 2017 .

[19]  G. Blomgren The development and future of lithium ion batteries , 2017 .

[20]  Peter Lamp,et al.  Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction. , 2015, Chemical reviews.

[21]  T. Sakai,et al.  Reliable Hydrogel with Mechanical “Fuse Link” in an Aqueous Environment , 2015, Advanced materials.

[22]  Lynden A. Archer,et al.  Suppression of lithium dendrite growth using cross-linked polyethylene/poly(ethylene oxide) electrolytes: a new approach for practical lithium-metal polymer batteries. , 2014, Journal of the American Chemical Society.

[23]  J. Gong,et al.  Fracture energy of polymer gels with controlled network structures. , 2013, The Journal of chemical physics.

[24]  T. Sakai,et al.  Mechanical Properties of Polymer Gels with Bimodal Distribution in Strand Length , 2013 .

[25]  T. Sakai,et al.  Ultimate elongation of polymer gels with controlled network structure , 2013 .

[26]  Kazunori Takada,et al.  Progress and prospective of solid-state lithium batteries , 2013 .

[27]  J. Gong,et al.  Transition between Phantom and Affine Network Model Observed in Polymer Gels with Controlled Network Structure , 2013 .

[28]  Diego Lisbona,et al.  A review of hazards associated with primary lithium and lithium-ion batteries , 2011 .

[29]  Yuki Kato,et al.  A lithium superionic conductor. , 2011, Nature materials.

[30]  T. Sakai,et al.  Structure and physical properties of dried Tetra-PEG gel , 2011 .

[31]  T. Sakai,et al.  Highly Elastic and Deformable Hydrogel Formed from Tetra-arm Polymers. , 2010, Macromolecular rapid communications.

[32]  Luzhuo Chen,et al.  Highly flexible and all-solid-state paperlike polymer supercapacitors. , 2010, Nano letters.

[33]  T. Sakai,et al.  Evaluation of Gelation Kinetics of Tetra-PEG Gel , 2010 .

[34]  Yuki Yamada,et al.  Kinetics of lithium ion transfer at the interface between graphite and liquid electrolytes: effects of solvent and surface film. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[35]  Philippe Knauth,et al.  Inorganic solid Li ion conductors: An overview , 2009 .

[36]  Yuji Yamamoto,et al.  Design and Fabrication of a High-Strength Hydrogel with Ideally Homogeneous Network Structure from Tetrahedron-like Macromonomers , 2008 .

[37]  Hiroyuki Nishide,et al.  Toward Flexible Batteries , 2008, Science.

[38]  M. Armand,et al.  Building better batteries , 2008, Nature.

[39]  Moon Jeong Park,et al.  Effect of molecular weight on the mechanical and electrical properties of block copolymer electrolytes , 2007 .

[40]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[41]  P. Johansson,et al.  Modelling lithium ion transport in helical PEO by ab initio calculations , 2001 .

[42]  M. Watanabe,et al.  XPS study of lithium surface after contact with lithium-salt doped polymer electrolytes , 2001 .

[43]  V. Noto,et al.  Ion−Oligomer Interactions in Poly(ethylene glycol)400/(LiCl)x Electrolyte Complexes , 1999 .

[44]  Toshiyuki Watanabe,et al.  High Ionic Conductivity of Polyether-Based Network Polymer Electrolytes with Hyperbranched Side Chains , 1999 .

[45]  C. Wan,et al.  Review of gel-type polymer electrolytes for lithium-ion batteries , 1999 .

[46]  B. Scrosati,et al.  Nanocomposite polymer electrolytes for lithium batteries , 1998, Nature.

[47]  Shinzo Kohjiya,et al.  High ionic conductivity of new polymer electrolytes based on high molecular weight polyether comb polymers , 1998 .

[48]  M. Armand,et al.  New solvating cross-linked polyether for lithium batteries , 1995 .

[49]  S. Besner,et al.  Comparative study of poly(ethylene oxide) electrolytes made with LiN(CF3SO2)2, LiCF3SO3 and LiClO4: Thermal properties and conductivity behaviour , 1992 .

[50]  M. Armand,et al.  Electrochemical study of linear and crosslinked POE-based polymer electrolytes , 1992 .

[51]  N. Ogata,et al.  Ionic Conductivity of Network Polymers from Poly(ethylene oxide) Containing Lithium Perchlorate , 1986 .

[52]  Michel Armand,et al.  Polymer solid electrolytes - an overview , 1983 .