Covalently cross-linked polymer stabilized electrolytes with self-healing performance <i>via</i> boronic ester bonds

Li, Sibo; Zuo, Cai; Zhang, Yong; Wang, Jirong; Gan, Hu; Li, Shaoqiao; Yu, Li‐Ping; Zhou, Binghua; Xue, Zhigang

doi:10.1039/d0py00728e

Cited by 43 publications

(31 citation statements)

References 63 publications

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“…In the SIPEs, anions are immobilized by covalently bonding with the polymeric backbones or by anion trapping agents so that the lithium ions associate with anions loosely by electrostatic interactions, resulting in a lithium-ion transference number of nearly close to 1. − Despite abovementioned advantages of SIPEs, most of them suffer from cracks during the electrochemical process of LMBs. Therefore, the self-healing polymer electrolytes would be an effective strategy to heal cracks and restore its original property for LMBs. − Polymer electrolytes with self-healing properties can be defined as dynamic covalent bond interactions and nondynamic covalent bond interactions. Jo et al designed and synthesized the self-healing SPEs with disulfide bond and hydrogen bond interactions.…”

Section: Introductionmentioning

confidence: 99%

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Self-Healing Single-Ion Conducting Polymer Electrolyte Formed via Supramolecular Networks for Lithium Metal Batteries

Gan

Zhang

et al. 2020

ACS Appl. Energy Mater.

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Polymer electrolytes (PEs) have been intensively researched in lithium metal batteries (LMBs) due to their good chemical stability, well compatibility with lithium metal electrodes, and high safety. Nevertheless, the typical PEs are dual-ion conductors, which usually suffer from the concentration polarization and cracks. Here, the self-healing single-ion conducting polymer electrolytes (SIPEs) are fabricated to reduce concentration polarization, leading to the suppression of the formation of lithium dendrites and healing of the cracks. The SIPEs are synthesized via reversible addition−fragmentation chain transfer copolymerization of lithium 4-styrenesulfonyl(phenylsulfonyl)imide, 2-(3-(6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl)ureido)ethyl methacrylate, and poly(ethylene glycol) methyl ether methacrylate in the absence of additional lithium salts. The obtained PEs (SIPE-5) show a good thermal stability up to 278.4 °C, comparatively high ionic conductivity up to 1.40 × 10 −5 S cm −1 at 60 °C, high lithium-ion transference number (t Li + = 0.89), and good compatibility with the lithium metal anode. The symmetric Li/Li cell remains an extremely stable and low overpotential without short circuiting over the 2800 h cycle at a current density of 0.05 mA cm −2 . The Li/LiFePO 4 coin cell also exhibits good cycling stability and superior rate performance. Therefore, the synthesized SIPEs possess the potential of the application in LMBs.

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Section: Introductionmentioning

confidence: 99%

“…The healed SPE displays no changes in the electrochemical performance of a battery. Li et al , reported boronic ester bonds and boroxine bonds in SPEs with healable properties. The boronic ester and boroxine-based SPEs presented excellent healable properties, high ionic conductivity, and good mechanical strength.…”

Section: Introductionmentioning

confidence: 99%

Self-Healing Single-Ion Conducting Polymer Electrolyte Formed via Supramolecular Networks for Lithium Metal Batteries

Gan

Zhang

et al. 2020

ACS Appl. Energy Mater.

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“…olefin metathesis), 1,[33][34][35] acetals, 36 transesterifications (incl. boronates), [37][38][39][40][41][42][43] and reactions involving disulfides. 12,44 Among these, reactions that can generate carbon-carbon bonds are of special interest since transformations are responsible for building up the carbon backbone of organic molecules and materials.…”

Section: Introductionmentioning

confidence: 99%

Polymerization, Stimuli-induced Depolymerization, and Precipitation-driven Macrocyclization in a Nitroaldol Reaction System

Ramström

2022

Preprint

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Dynamic covalent polymers of different topology have been synthesized from an aromatic dialdehyde and α,ω-dinitroalkanes via the nitroaldol reaction. All dinitroalkanes yielded dynamers with the dialdehyde, where the length of the dinitroalkane chain played a vital role in determining the structure of the final products. For longer dinitroalkanes, linear dynamers were produced, where the degree of polymerization reached a plateau at higher feed concentrations. In the reactions involving 1,4-dinitrobutane and 1,5-dinitropentane, specific macrocycles were formed through depolymerization of the linear chains, further driven by precipitation. At lower temperature, the same systemic self-sorting effect was also observed for the 1,6-dinitrohexane-based dynamers. Moreover, the dynamers showed a clear adaptive behavior, displaying depolymerization and rearrangement of the dynamer chains in response to alternative building blocks as external stimuli.

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“…To satisfy the increasing demand for energy storage devices such as portable electronic products and electric vehicles, the rechargeable lithium metal batteries (LMBs) have been widely applied in the field of energy storage due to their properties of light weight, high gravimetric energy densities, and long cycle life. − The electrolyte is an important component of LMBs, which could play a crucial part in fast conduction of lithium ions and the electrochemical performance of LMBs. − However, the commercial LMBs usually suffer from the potential safety issues such as flammability, leakage, and poor chemical stability because the liquid electrolytes consist of the organic carbonate solvents and lithium salt. − To address the aforementioned problems, solid polymer electrolytes (SPEs) composed of a polymer host and disassociated lithium salt are used as effective alternatives for liquid electrolytes to alleviate the safety issues. Nevertheless, the relatively low ionic conductivity (<10 –6 S cm –1 ) of SPEs at room temperature prevents their extensive application in LMBs, especially for the most widely used poly(ethylene oxide) (PEO)-based SPEs. − The PEO-based SPEs usually have low ionic conductivity, which is ascribed to the semicrystalline region in the polymer matrix. Moreover, the poor contact interfaces between SPEs and solid electrodes could result in the deteriorated cycling performance. − …”

Section: Introductionmentioning

confidence: 99%

Fabrication of Borate-Based Porous Polymer Electrolytes Containing Cyclic Carbonate for High-Performance Lithium Metal Batteries

Zhou

Lai

et al. 2021

ACS Appl. Energy Mater.

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A series of borate-based porous polymer electrolytes (B-PPEs) is prepared by incorporating the copolymers containing cyclic boroxine and cyclic carbonate groups into poly(vinylidene fluoride) (PVDF) through the phase inversion method. The dense and well-interconnected pores are obtained in the polymer matrix when the content of the copolymer reached 40 wt %. The ethylene–oxygen chain segments in the copolymer can facilitate the mobility of polymer chains and form the uniform distribution of pores in the B-PPEs. The B-PPEs show an enhanced ionic conductivity of 1.32 × 10–3 S cm–1 at 30 °C, which is due to the uniform well-interconnected pores in the polymer host. The cyclic carbonate units interact with the liquid electrolyte, which could improve the electrolyte uptake capacity of the polymer matrix. Benefited from the Lewis acid–base interactions between boron moieties and the anions of the lithium salt, the lithium-ion transference number of B-PPEs is also significantly improved. Compared to the pure PVDF-based electrolyte, the Li/B-PPEs/Li cell displays a very stable polarization voltage and the long-time cycling for 1000 h at a current density of 0.2 mA cm–2. Moreover, the Li/B-PPEs/LiFePO4 cells deliver a higher capacity of 143.0 mAh g–1 at 0.2 C and 86% capacity retention after 150 cycles. The B-PPEs could be a promising candidate for enhancing the safety and electrochemical properties of lithium metal batteries.

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Covalently cross-linked polymer stabilized electrolytes with self-healing performance via boronic ester bonds

Abstract: Herein, the solid polymer electrolytes (SPEs) were designed and fabricated via the photopolymerization of the macromolecular crosslinker with boronic ester bonds and poly(ethylene glycol) diacrylate (PEGDA) with different molecular weights...

Cited by 43 publications

References 63 publications

Self-Healing Single-Ion Conducting Polymer Electrolyte Formed via Supramolecular Networks for Lithium Metal Batteries

Self-Healing Single-Ion Conducting Polymer Electrolyte Formed via Supramolecular Networks for Lithium Metal Batteries

Polymerization, Stimuli-induced Depolymerization, and Precipitation-driven Macrocyclization in a Nitroaldol Reaction System

Fabrication of Borate-Based Porous Polymer Electrolytes Containing Cyclic Carbonate for High-Performance Lithium Metal Batteries

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