Preparation and properties of self‐healable solid‐state polymer electrolytes based on covalent adaptive networks enabled by disulfide bond

Abstract

Covalent adaptive networks (CANs) have numbers of versatile abilities derived from topological reshuffling with interesting potentials. Here, self-healable solid-state polymer electrolytes were developed by integrating epoxy-resinbased CANs enabled by disulfide bond with a solid lithium salt (LiTFSI). The disulfide bond was introduced by using a disulfide-containing aliphatic polyamine as the epoxy-curing agent. To determine the cure cycle of this epoxy-resin system, the curing kinetics in the presence of LiTFSI was studied by nonisothermal differential scanning calorimetry. The prepared ion-conducting (IC) CANs with different LiTFSI content were optically transparent and selfhealable at temperatures above glass transition temperature (T g ). The effect of LiTFSI content on the thermal stability and tensile properties was investigated.The electrical properties of the IC CANs were studied by impedance spectroscopy at various temperatures. Their ionic conductivity was analyzed by the Vogel-Tamman-Fulcher model and equivalent-circuit fitting. Due to the high mobility of charge carriers, the IC CAN sample (containing15 wt% LiTFSI) exhibited the best ionic conductivity, which reached a value of 3.35 Â 10 À6 S cm À1 at 80 C and 8.31 Â 10 À6 S cm À1 at 100 C, presenting great attraction for self-healing iontronics.

High‐performance healable plastics: Focusing topological structure design based on constitutional dynamic chemistry

“…Moreover, we have highlighted a range of toughening strategies that focus on introducing hierarchical dynamic bonds, constructing microphase separation structures, and implanting bionic architecture. Subsequently, our review also provides a summary of limited research reports on autonomously roomtemperature self-healing plastics, with the objective of 139 Copyright 2012, WILEY-VCH. (C) Schematic diagram of the Li + transport process and the protein chain immobilized by SPI through the interaction of positively charged amino acids with anionic species, thus facilitating the migration of Li + ions.…”

“…For example, Wu synthesized the robust solid polymer electrolyte (IC CANs) containing covalent adaptive networks, which crosslinked by disulfide bonds (Figure 14A). 139 In such a system, the optimal IC‐15 wt% CANs exhibited a notable T g value of 75°C (Figure 14B), which ensure the superior modulus that can effectively impede the proliferation of lithium dendrites during the long‐term charge–discharge cycling. Nevertheless, the elevated temperature enabled the thermal stability of the IC‐15 wt% CANs, while hindering the healability.…”

“…(A) Schematic diagram of solid‐state IC CANs. Reproduced with permission 139 . Copyright 2012, WILEY‐VCH.…”

“…(B) Temperature dependent of Storage modulus profiles for CANs and IC‐15 wt% CANs. Reproduced with permission 139 . Copyright 2012, WILEY‐VCH.…”

Self-Healing Polymer Electrolytes for Next-Generation Lithium Batteries

“…In addition, RFSPE-3 showed an inhibitory effect on the growth of lithium dendrites, which resulted in a cycling stability for up to 1800 h at 1 mAh/cm 2 . A somewhat similar approach for the incorporation of disulfide dynamic networks into epoxy matrix was followed by Sun and Wu (see Table 1, entry 15) [82]. The disulfide bond was introduced using a disulfide-containing aliphatic polyamine as the epoxy-curing agent.…”