One‐Step In Situ Polymerization: A Facile Design Strategy for Block Copolymer Electrolytes

Guo, Kairui; Wang, Jirong; Shi, Zhen; Wang, Yong; Xie, Xiaolin; Xue, Zhigang

doi:10.1002/ange.202213606

“…The glass-transition temperature (T g ) greatly affects the chain segment movement of solid polymer electrolytes. 40,51 Thus, decreasing the T g of SPEs is an effective way to promote Li + conduction. Differential scanning calorimetry (DSC) was conducted to measure the T g values of the prepared SPEs, and GPA exhibited a T g value of −40.3 °C.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Boronic Ester Transesterification Accelerates Ion Conduction for Comb-like Solid Polymer Electrolytes

Wang

¹

,

Shi

²

,

Guo

³

et al. 2023

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Polyether is a kind of ideal polymer matrix for solid polymer electrolytes (SPEs), but its inherent drawbacks (such as the semi-crystalline nature and strong complexation of lithium ions) still hinder their commercial application. The construction of comb-like SPEs effectively increases their functionalities and improves the comprehensive performance. Herein, we apply a dynamic boronic ester exchange strategy to simultaneously enhance the lithium-ion conduction and self-healing ability of the SPEs, thus effectively solving the current problems of polyether. The copolymer (GPA) containing side chains with poly(ethylene glycol) (PEG) and diol groups was obtained through reversible addition–fragmentation chain-transfer (RAFT) polymerization and hydrolysis, and PBA-M2070 containing the boronic acid group and flexible polyether segments was obtained via Schiff base reaction. Boronic ester bonds were formed by dehydration of the diol groups of GPA and the boronic acid groups of PBA-M2070. Dynamic exchange of the boronic ester bonds at the branched sites enhanced the side-chain motion, thus increasing the self-healing ability and electrochemical performance of the SPEs, as well as the cycling stability of assembled batteries. Benefiting from the dynamic boronic ester exchange and enhanced side-chain mobility, the SPEs exhibited self-healing within 10 min and an ionic conductivity of 1.58 × 10–5 S cm–1 at 30 °C. The assembled lithium metal batteries (LMBs) were operated stably at 0.5C for 300 cycles. The dynamic boronic ester exchange strategy used to enhance the LMBs properties provides new insight into the design of comb-like polymer electrolytes.

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Efficiencies of Various in situ Polymerizations of Liquid Electrolytes and the Practical Implications for Quasi Solid‐state Batteries

Li,

Wang,

Hao

et al. 2023

Angewandte Chemie

0

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In situ polymerization of liquid electrolytes is currently the most feasible way for constructing solid‐state batteries, which, however, is affected by various interfering factors of reactions and so the electrochemical performance of cells. To disclose the effects from polymerization conditions, two types of generally used in situ polymerizing reactions of ring‐opening polymerization (ROP) and double bond radical polymerization (DBRP) were investigated on the aspects of monomer conversion and electrochemical properties (Li+‐conductivity and interfacial stability). The ROP generated poly‐ester and poly‐carbonate show a high monomer conversion of ≈90 %, but suffer a poor Li+‐conductivity of lower than 2×10−5 S cm−1 at room temperature (RT). Additionally, the terminal alkoxy anion derived from the ROP is not resistant to high‐voltage cathodes. While, the DBRP produced poly‐VEC(vinyl ethylene carbonate) and poly‐VC(vinylene carbonate) show lower monomer conversions of 50–80 %, delivering relatively higher Li+‐conductivities of 2×10−4 S cm−1 at RT. Compared two polymerizing reactions and four monomers, the VEC‐based F‐containing copolymer possesses advantages in Li+‐conductivity and antioxidant capacity, which also shows simultaneous stability towards Li‐metal with the help of LiF‐based passivating layer, allowing a long‐term stable cycling of high‐voltage quasi solid‐state cells.

show abstract

Efficiencies of Various in situ Polymerizations of Liquid Electrolytes and the Practical Implications for Quasi Solid‐state Batteries

Li,

Wang,

Hao

et al. 2023

View full text Add to dashboard Cite

In situ polymerization of liquid electrolytes is currently the most feasible way for constructing solid‐state batteries, which, however, is affected by various interfering factors of reactions and so the electrochemical performance of cells. To disclose the effects from polymerization conditions, two types of generally used in situ polymerizing reactions of ring‐opening polymerization (ROP) and double bond radical polymerization (DBRP) were investigated on the aspects of monomer conversion and electrochemical properties (Li+‐conductivity and interfacial stability). The ROP generated poly‐ester and poly‐carbonate show a high monomer conversion of ≈90 %, but suffer a poor Li+‐conductivity of lower than 2×10−5 S cm−1 at room temperature (RT). Additionally, the terminal alkoxy anion derived from the ROP is not resistant to high‐voltage cathodes. While, the DBRP produced poly‐VEC(vinyl ethylene carbonate) and poly‐VC(vinylene carbonate) show lower monomer conversions of 50–80 %, delivering relatively higher Li+‐conductivities of 2×10−4 S cm−1 at RT. Compared two polymerizing reactions and four monomers, the VEC‐based F‐containing copolymer possesses advantages in Li+‐conductivity and antioxidant capacity, which also shows simultaneous stability towards Li‐metal with the help of LiF‐based passivating layer, allowing a long‐term stable cycling of high‐voltage quasi solid‐state cells.

show abstract

One‐Step In Situ Polymerization: A Facile Design Strategy for Block Copolymer Electrolytes

Cited by 3 publications

References 101 publications

Boronic Ester Transesterification Accelerates Ion Conduction for Comb-like Solid Polymer Electrolytes

Boronic Ester Transesterification Accelerates Ion Conduction for Comb-like Solid Polymer Electrolytes

Efficiencies of Various in situ Polymerizations of Liquid Electrolytes and the Practical Implications for Quasi Solid‐state Batteries

Efficiencies of Various in situ Polymerizations of Liquid Electrolytes and the Practical Implications for Quasi Solid‐state Batteries

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