A novel single-ion conducting polymer electrolyte (SIPE) membrane with high lithium-ion transference number, good mechanical strength, and excellent ionic conductivity is designed and synthesized by facile coupling of lithium bis(allylmalonato) borate (LiBAMB), pentaerythritol tetrakis (2-mercaptoacetate) (PETMP) and 3,6-dioxa-1,8-octanedithiol (DODT) in an electrospun poly(vinylidienefluoride) (PVDF) supporting membrane via a one-step photoinitiated in situ thiol-ene click reaction. The structure-optimized LiBAMB-PETMP-DODT (LPD)@PVDF SIPE shows an outstanding ionic conductivity of 1.32 × 10 S cm at 25 °C, together with a high lithium-ion transference number of 0.92 and wide electrochemical window up to 6.0 V. The SIPE exhibits high tensile strength of 7.2 MPa and elongation at break of 269%. Due to these superior performances, the SIPE can suppress lithium dendrite growth, which is confirmed by galvanostatic Li plating/stripping cycling test and analysis of morphology of Li metal electrode surface after cycling test. Li|LPD@PVDF|Li symmetric cell maintains an extremely stable and low overpotential without short circuiting over the 1050 h cycle. The Li|LPD@PVDF|LiFePO cell shows excellent rate capacity and outstanding cycle performance compared to cells based on a conventional liquid electrolyte (LE) with Celgard separator. The facile approach of the SIPE provides an effective and promising electrolyte for safe, long-life, and high-rate lithium metal batteries.
We disclose an efficient catalyst system of commercial ureas/alkoxides for the challenging ring-opening polymerization (ROP) of bioderived "nonpolymerizable" γbutyrolactone (γ-BL). This effective polymerization can not only be performed under mild conditions like bulk polymerization, higher monomer ratio, and elevated temperature (−20 °C comparing to −40 °C), but also obtains high-molecular-weight poly(γ-butyrolactone) (PγBL) (M n up to 68.2 kg/mol). To our knowledge, this is a big progress in the research area of ROP of γ-BL, which provides a promising prospect for the industrial-scale methodology of PγBL production. Structural analysis including NMR and MALDI-TOF, along with mechanistic computational studies based on DFT calculations, show that urea anion acts as a bifunctional catalyst, which activates the alcohol initiator and γ-BL before obeying an anionic polymerization. Furthermore, the catalytic activities of ureas/alkoxides systems have been optimized using the ureas with electron-donating groups which are proved to have lower activation barrier by computational calculation.
With the rapid development of electronic devices and electric vehicles, the requirements for their safety issues and service stabilities have become more and more strict.
due to its intrinsic thermodynamics instability. [4][5][6][7][8] The dissolution issue of cathode material (manganese-based oxides, vanadium-based compounds, polyoxometalate [POM] clusters, etc.) directly causes severe performance deterioration in aqueous batteries. [5,[9][10][11] Especially, high-nuclearity POMs with reversible multielectron redox chemistry have demonstrated some promise as Zn 2+ host in AZIBs, but still suffer from severe capacity fading due to their water-soluble feature. [7,11,12] A stable cathode electrolyte interface (CEI) is generally useful in stabilizing the conventional cathodes in aqueous electrolytes. [10,13] Zhou et al. demonstrated a CEI layer of CaSO 4 •2H 2 O formed on the surface of Ca 2 MnO 4 to effectively suppress material dissolution via an electrochemically charging process. [4] Yet the developmental CEI for POM-based cathodes is still absent to date. To broaden the feasibility of POM-based electrodes in AZIBs, it should be charming and economical if a protective CEI can be constructed in situ to stabilize the POM-based cathodes.Besides the cathode dissolution, other fatal issues, including an unstable electrolyte environment due to the parasitic H 2 O ionization and metallic Zn anode stemming from uncontrollable dendrite formation, have hindered the development of AZIBs. [3,14,15] Various Zn anode stabilization strategies, including building Zn anode protective layers, [16] regulating Despite a promising outlook due to the intrinsic low cost and high safety, the practical application of aqueous Zn-ion battery is impeded by the severe mutual problems of cathode dissolution, electrolyte parasitic reactions, and metallic anode dendrite growth. Herein, a triple-functional strategy is proposed that a polyoxovanadate (POV) cluster of K 10 [V IV 16 V V 18 O 82 ] as a promising Zn 2+ host can concomitantly stabilize the cluster cathode, aqueous electrolyte, and metallic Zn anode. An in situ generated cathode electrolyte interface via anodic oxidation is identified as effective in preventing the dissolution of POV cathode. Molecular dynamics simulation and density functional theory calculation confirm that the [V IV 16 V V 18 O 82 ] 10− polyoxoanions can synergistically suppress electrolyte side reactions by modulating the primary solvation shell of Zn 2+ -6H 2 O, and random anode dendrite growth by in situ constructing a stable solid electrolyte interface of Zn-POV. As a result, the Zn//POV battery exhibits unprecedented cycling durability over 10 000 cycles at high rates of 5 and 12 A g −1 . In a systematic consideration, the findings enlighten the origin of triple-functional polyoxometalates and will significantly propel the practical development of aqueous batteries.
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