Disulfide bond-embedded polyurethane solid polymer electrolytes with self-healing and shape-memory performance

Huang, Yingjie; Wang, Jirong; Shi, Zhen; Wang, Hongli; Xue, Zhigang

doi:10.1039/d2py00944g

Cited by 9 publications

(2 citation statements)

References 55 publications

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“…However, the insufficient ion conduction and low t Li + of these SPEs constructed with dynamic noncovalent bonding prove that overcoming the inherent limitations of PEO is still difficult. For dynamic covalent bonding systems (disulfide bonds, − boroxine bonds, , boronic ester bonds, imine bonds, − ionic bonds, − and D-A reaction), the exchange reactions between the dynamic covalent bonds not only enable self-healing but also reduce the crystallinity of PEO . There are two guidelines for evaluating the dynamic covalent bonds in SPEs: (1) low bond energy and (2) excellent temperature response.…”

Section: Introductionmentioning

confidence: 99%

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

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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Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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“…Solid-state electrolytes have been investigated extensively as potentially safer alternatives to flammable and toxic liquid electrolytes − and exhibit good interfacial contact with electrodes. − Poly(ethylene oxide) (PEO) is a common chemical motif known to facilitate lithium ion transport by ion coordination with the backbone ether oxygens. − Although PEO-based polymer electrolytes show high ionic conductivity, , these materials exhibit relatively low conductivity at room temperature and a strong temperature-dependent modulus that drops substantially upon heating. − To enhance their mechanical properties, PEO can be covalently or noncovalently cross-linked, leading to rubbery electrolytes (characteristic plateau modulus ∼0.1 MPa) with suppressed dendrite formation due to the nanoscale mesh size in cross-linked PEO. ,, However, covalent permanent networks are not easily reprocessed or recycled after the curing processes. In recent years, vitrimers have received increased attention as robust and recyclable solid polymer electrolytes. − Various dynamic bonds such as boronic ester, ,,, imine, − ,, vinylogous urethane, boroxine, and disulfide ,,− have been previously incorporated into vitrimers for solid-state electrolyte applications. Soy protein-based imine (SPI) dynamic networks were prepared by the Fang group .…”

Section: Introductionmentioning

confidence: 99%

Control of Lithium Salt Partitioning, Coordination, and Solvation in Vitrimer Electrolytes

Jang,

Hernandez Alvarez,

Chen

et al. 2023

Chem. Mater.

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Vitrimers are an important class of materials offering advantages over conventional thermosets due to their self-healing properties and reprocessability. Vitrimers are ideal candidate materials for solid polymer electrolytes because their viscoelasticity and conductivity can be independently tuned by salt addition in distinct ways from linear polymer electrolytes while further providing resistance to lithium dendrite propagation. In this work, the chemical and physical properties of vinylogous urethane (VU) vitrimers were characterized by using a combination of experiments and simulations to develop molecular design rules for controlling material properties. A series of VU vitrimers containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were synthesized by precisely controlling the VU cross-linking density using defined linker lengths of ethylene glycol (xEG, x = 2, 3, 4, 6, or 12), thereby enabling control over the dynamic bond-to-EG ratio. Viscoelastic measurements show that the characteristic relaxation time τ* of VU vitrimers containing salt decreased by a factor of ∼70 relative to neutral vitrimers due to Li-ion coordination and catalysis of VU bond exchange. Stress relaxation times and shear moduli decrease with lower cross-linking densities in VU vitrimers. Solid-state 7 Li NMR further reveals that VU vitrimers with longer linker lengths prefer lithium-ethylene oxide (Li-EO) solvation, whereas shorter linkers cannot sufficiently solvate the cation, and Li-VU coordination is preferred. Density functional theory (DFT) simulations were used to elucidate the dominant binding mode of Li-ion interaction as a function of linker length. The preferential partitioning of Li at the VU site leads to an order of magnitude decrease in stress relaxation times with a negligible impact on the conductivity after normalizing to the glass transition temperature T g . Interestingly, our results show universal behavior for T g -normalized ionic conductivity data regardless of linker length. Overall, this work provides new avenues for orthogonal tuning of bulk dynamics, recyclability, and conductivity in vitrimer electrolytes.

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Construction and mechanism of phase-locked structured PU elastomers with tunable mechanical and self-healing properties

Jiang,

Pang,

Cheng

et al. 2024

Applied Surface Science

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Disulfide bond-embedded polyurethane solid polymer electrolytes with self-healing and shape-memory performance

Abstract: In order to improve the ability to confronting the deformation and fracture damage of polymer electrolytes, thus providing high safety for flexible batteries, solid-state polymer electrolytes with both self-healing and...

Cited by 9 publications

References 55 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

Control of Lithium Salt Partitioning, Coordination, and Solvation in Vitrimer Electrolytes

Construction and mechanism of phase-locked structured PU elastomers with tunable mechanical and self-healing properties

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