One-Pot Synthesis of Polyester-Based Linear and Graft Copolymers for Solid Polymer Electrolytes

Guo, Kairui; Li, Shaoqiao; Gong, Chen; Wang, Jirong; Wang, Yong; Xie, Xiaolin; Xue, Zhigang

doi:10.31635/ccschem.021.202101364

“…The ionic conductivity of BCPE12 at ambient temperature was 2.57×10 −5 S cm −1 , which is quite close to that of BCPE4 (3.14×10 −5 S cm −1 ). This might be ascribed to the high structural similarity and similar thermodynamic behavior of PVL ( T g =−62 °C, T m =58 °C) compared to PCL [14c] . The ionic conductivity of BCPE13 based on polycarbonate blocks at ambient temperature was slightly lower than that of BCPE4 based on polyester blocks, which was 7.16×10 −6 S cm −1 .…”

Section: Resultsmentioning

confidence: 90%

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

Guo

¹

,

Wang

²

,

Shi

³

et al. 2023

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To optimize the rapid transport of lithium ions (Li+) inside lithium metal batteries (LMBs), block copolymer electrolytes (BCPEs) have been fabricated in situ in LMBs via a one‐step method combining reversible addition‐fragmentation chain transfer (RAFT) polymerization and carboxylic acid‐catalyzed ring‐opening polymerization (ROP). The BCPEs balanced the Li+ coordination characteristics of the polyether‐ and polyester‐based electrolytes to achieve a rapid Li+ migration in the SPEs. The carboxylic acid played a dual role since it both catalyzed the ROP and stabilized the interface. Furthermore, the in situ assembly of LMBs did effectively enable an efficient intercalation/de‐intercalation of Li+ at the electrode/electrolyte interface. The in situ assembled Li/BCPE4/LFP exhibited high‐capacity retention of 92 % after 400 cycles at 1 C. The one‐step in situ fabrication of BCPEs provides a new direction for the design of polymer electrolytes.

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“…However, the peak of PAA 25 ‐ co ‐PPEGA 50 disappeared completely, which was attributed to the brush‐shaped structure of PPEGA destroying the crystallinity of PEO, resulting in the change of PEO into an amorphous structure. Furthermore, the XRD pattern of PAA 25 ‐ b ‐PCL 150 contained the typical Bragg reflections of PCL polymers at 2 θ =21° (110), 21.2° (111) and 23 °C (200) [14c] . Upon the introduction of PEG, the diffraction peaks of PCL were suppressed to a certain extent.…”

Section: Resultsmentioning

confidence: 99%

“…The ionic conductivity of BCPE13 based on polycarbonate blocks at ambient temperature was slightly lower than that of BCPE4 based on polyester blocks, which was 7.16×10 −6 S cm −1 . This is because the PTMC segment with higher T g (−16 °C) is less flexible than PEO and PCL, [14c] which makes the ionic conductivity of PTMC‐based electrolytes to be extremely low (10 −7 S cm −1 ) at ambient temperature.…”

Section: Resultsmentioning

confidence: 99%

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

Guo

¹

,

Wang

²

,

Shi

³

et al. 2023

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To optimize the rapid transport of lithium ions (Li+) inside lithium metal batteries (LMBs), block copolymer electrolytes (BCPEs) have been fabricated in situ in LMBs via a one‐step method combining reversible addition‐fragmentation chain transfer (RAFT) polymerization and carboxylic acid‐catalyzed ring‐opening polymerization (ROP). The BCPEs balanced the Li+ coordination characteristics of the polyether‐ and polyester‐based electrolytes to achieve a rapid Li+ migration in the SPEs. The carboxylic acid played a dual role since it both catalyzed the ROP and stabilized the interface. Furthermore, the in situ assembly of LMBs did effectively enable an efficient intercalation/de‐intercalation of Li+ at the electrode/electrolyte interface. The in situ assembled Li/BCPE4/LFP exhibited high‐capacity retention of 92 % after 400 cycles at 1 C. The one‐step in situ fabrication of BCPEs provides a new direction for the design of polymer electrolytes.

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“…Li et al constructed self-healing cross-linked SPEs with boronic ester bonds that achieved self-healing at 60 °C for 0.5 h and exhibited higher ionic conductivities than their counterparts without boronic ester bonds . To our knowledge, compared with cross-linked structures, the brush structures of the comb-like SPEs are more conducive to promoting the movement of chain segments, thus enhancing ionic conduction. − Notably, the enhanced ion conduction seen with SPEs is inadvertently ignored when the boronic ester is introduced into SPEs with dynamic covalent bonds. Most importantly, the grafted segments containing boronic esters endow polyether-based SPEs with high ionic conductivity and t Li + value, and they facilitate the dissociation of lithium salts. − …”

Section: Introductionmentioning

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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One-Pot Synthesis of Polyester-Based Linear and Graft Copolymers for Solid Polymer Electrolytes

Cited by 18 publications

References 83 publications

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

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

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

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

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