A rigid-flexible coupling poly(vinylene carbonate) based cross-linked network: A versatile polymer platform for solid-state polymer lithium batteries

Dong, Ting; Zhang, Huanrui; Hu, Renjie; Mu, Pengzhou; Liu, Zhi; Du, Xiaofan; Lu, Chenglong; Lu, Guoli; Liu, Wei; Cui, Guanglei

doi:10.1016/j.ensm.2022.05.052

Cited by 38 publications

(25 citation statements)

References 38 publications

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“…That is, the currently reported SPEs are being restricted by either low Li + -conductivity or poor interfacial stability with anode or high-voltage cathode. [8,9] To obtain the desired high-per-formance SPE with both high Li + conductivity and wide electrochemical window, it is necessary to understand the influencing factors on the Li + -conductivity of SPE and the electrochemical window, respectively.…”

Section: Introductionmentioning

confidence: 99%

Influencing Factors on Li‐ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes, Exampled by Polycarbonates, Polyoxalates and Polymalonates

Xie

Wang

et al. 2023

Angew Chem Int Ed

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The application of solid polymer electrolytes (SPEs) in all‐solid‐state(ASS) batteries is hindered by lower Li+‐conductivity and narrower electrochemical window. Here, three families of ester‐based F‐modified SPEs of poly‐carbonate (PCE), poly‐oxalate (POE) and poly‐malonate (PME) were investigated. The Li+‐conductivity of these SPEs prepared from pentanediol are all higher than the counterparts made of butanediol, owing to the enhanced asymmetry and flexibility. Because of stronger chelating coordination with Li+, the Li+‐conductivity of PME and POE is around 10 and 5 times of PCE. The trifluoroacetyl‐units are observed more effective than −O−CH2−CF2−CF2−CH2−O− during the in situ passivation of Li‐metal. Using trifluoroacetyl terminated POE and PCE as SPE, the interfaces with Li‐metal and high‐voltage‐cathode are stabilized simultaneously, endowing stable cycling of ASS Li/LiNi0.6Co0.2Mn0.2O2 (NCM622) cells. Owing to an enol isomerization of malonate, the cycling stability of Li/PME/NCM622 is deteriorated, which is recovered with the introduce of dimethyl‐group in malonate and the suppression of enol isomerization. The coordinating capability with Li+, molecular asymmetry and existing modes of elemental F, are all critical for the molecular design of SPEs.

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Section: Introductionmentioning

confidence: 99%

Influencing Factors on Li‐ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes, Exampled by Polycarbonates, Polyoxalates and Polymalonates

Xie

Wang

et al. 2023

Angew Chem Int Ed

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“…Recent research shows that the solid-state polymer electrolyte (SPE) is a promising replacement of flammable liquid electrolytes due to its inherent nonleakage and improved safety performance. − However, the ionic conductivity is relatively poor, which is generally much smaller than 10 –4 S·cm –1 at ambient temperature. Therefore, the SPE-based batteries usually demand higher work temperature, making them far from satisfying the needs for practical applications.…”

Section: Introductionmentioning

confidence: 99%

In-Situ Formed Phosphorus Modified Gel Polymer Electrolyte with Good Flame Retardancy and Cycling Stability for Rechargeable Lithium Batteries

Xie

Liu

et al. 2023

ACS Sustainable Chem. Eng.

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The gel polymer electrolyte (GPE) is a promising substitution for traditional liquid electrolytes. However, GPE is still troubled mainly by its sluggish ionic conductivity and inferior interfacial compatibility with electrodes. Herein, a phosphorus-modified GPE was fabricated by in situ incorporation of black phosphorus (BP) nanosheets into a poly(methyl methacrylate) (PMMA) matrix during the self-polymerization of monomers. The developed GPE exhibited high ionic conductivity (1.083 mS·cm–1 at 30 °C), an enhanced Li+ transference number (0.43), and a wide electrochemical stability window (5.2 V vs Li+/Li), while good thermal stability and improved flame retardancy can also be achieved. Differential scanning calorimeter measurements confirmed that the crystallinity of the PMMA matrix was not changed as BP nanosheets were incorporated. Further investigation proved that BP nanosheets contained in PMMA segments effectively immobilized the anions to decrease the coordination number around Li+. As a result, Li+ ion transport through the GPE was facilitated, which promoted the uniform stripping/plating of lithium while cycling the lithium symmetry cell. Based on the phosphorus-modified GPE, the Li|LiFePO4 and Li|LiNi0.5Co0.2Mn0.3O2 batteries and graphite|LiFePO4 soft-package battery exhibited encouraging electrochemical performances and safety properties.

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“…Therefore, it is quite significant to reduce the thickness of the SSEs for developing practical solid-state batteries. However, the mechanical strength of the SSEs may deteriorate with the thickness decreasing, which easily leads to lithium dendrites penetration. , Generally, using a strong ultrathin self-supporting host to design ultrathin electrolytes is quite essential to reduce the thickness of SPEs. − The self-supporting host with excellent mechanical strength such as polyethylene (PE) separator enables the ultrathin SPEs with high mechanical strength. For instance, an ultrathin, flexible, and mechanically strong SPE was synthesized by integrating the PE separator with PEO/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI), which exhibits good electrochemical performance .…”

Section: Introductionmentioning

confidence: 99%

Ultrathin and Robust Composite Electrolyte for Stable Solid-State Lithium Metal Batteries

Wang

Yang

et al. 2023

ACS Appl. Mater. Interfaces

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Solid-state polymer electrolytes (SPEs) are considered as one of the most promising candidates for the next-generation lithium metal batteries (LMBs). However, the large thickness and severe interfacial side reactions with electrodes seriously restrict the application of SPEs. Herein, we developed an ultrathin and robust poly(vinylidene fluoride) (PVDF)-based composite polymer electrolyte (PPSE) by introducing polyethylene (PE) separators and SiO2 nanoparticles with rich silicon hydroxyl (Si-OH) groups (nano-SiO2). The thickness of the PPSE is only 20 μm but possesses a quite high mechanical strength of 64 MPa. The introduction of nano-SiO2 fillers can tightly anchor the essential N,N-dimethylformamide (DMF) to reinforce the ion-transport ability of PVDF and suppress the side reactions of DMF with Li metal, which can significantly enhance the electrochemical stability of the PPSE. Meanwhile, the Si-OH groups on the surface of nano-SiO2 as a Lewis acid promote the dissociation of the lithium bis(fluorosulfonyl)imide (LiFSI) and immobilize the FSI– anions, achieving a high lithium transference number (0.59) and an ideal ionic conductivity (4.81 × 10–4 S cm–1) for the PPSE. The assembled Li/PPSE/Li battery can stably cycle for a record of 11,000 h, and the LiNi0.8Co0.1Mn0.1O2/PPSE/Li battery presents an initial specific capacity of 173.3 mA h g–1 at 0.5 C, which can stably cycle 300 times. This work provides a new strategy for designing composite solid-state electrolytes with high mechanical strength and ionic conductivity by modulating their framework.

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A rigid-flexible coupling poly(vinylene carbonate) based cross-linked network: A versatile polymer platform for solid-state polymer lithium batteries

Cited by 38 publications

References 38 publications

Influencing Factors on Li‐ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes, Exampled by Polycarbonates, Polyoxalates and Polymalonates

Influencing Factors on Li‐ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes, Exampled by Polycarbonates, Polyoxalates and Polymalonates

In-Situ Formed Phosphorus Modified Gel Polymer Electrolyte with Good Flame Retardancy and Cycling Stability for Rechargeable Lithium Batteries

Ultrathin and Robust Composite Electrolyte for Stable Solid-State Lithium Metal Batteries

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