Perovskite solar cells(PSCs)have become the promising next-generation photovoltaic devices due to their excellent photoelectric performances,and the power conversion efficiencies(PCEs)have experienced unprecedented ra...Perovskite solar cells(PSCs)have become the promising next-generation photovoltaic devices due to their excellent photoelectric performances,and the power conversion efficiencies(PCEs)have experienced unprecedented rapid increase in recent years.However,to realize the practical application of PSCs,high performance and long-term stability are required and the preparation of high-quality perovskite film is the key.Herein,we adopt a simple and effective method to prepare high-quality perovskite films by introducing the poly(vinylidene fluoride)(PVDF)polymer additive with abundant hydrophobic F.As the growth template,the PVDF promotes the growth of perovskite crystal,improves the crystallinity and film morphology,thus reducing defect density and inhibiting carrier recombination.The results show that the photovoltaic performances of the perovskite device with PVDF are meaningfully improved,and a high PCE of 21.42%is achieved with an improvement of 10.87%,More importantly,the PVDF-based perovskites display greatly enhanced humidity and heat stability due to the protection of strong hydrophobic barrier from F and PVDF long chain.Aging at 45%±5%relative humidity(RH)for 2400 h and 850 C for300 h,respectively,the unsealed PVDF devices can maintain over 90%of the initial PCE.It indicates that suitable polymer additives can improve the film quality to acquire high-performance and stable PSCs and lay a foundation to design new perovskite light absorption layer with different polymers for the further development of PSCs.展开更多
Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis...Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis.The degree of grafting (DG) of the grafted PVDF was determined by fluorine elemental analysis (FEA) method,and was compared with the DGs determined by weighing method,acid-base back titration method and quantitative FT-IR method.The results show that the FEA method is accurate,convenient and universal,especially for the grafted polymer powders.展开更多
Porous membranes were prepared using the phase inversion method from poly(vinylidene fluoride)-graftpoly(N-vinyl pyrrolidone)(PVDF-g-PVP) powders, which were synthesized via γ-ray induced graft polymerization(pre-irr...Porous membranes were prepared using the phase inversion method from poly(vinylidene fluoride)-graftpoly(N-vinyl pyrrolidone)(PVDF-g-PVP) powders, which were synthesized via γ-ray induced graft polymerization(pre-irradiation). Chemical compositions, thermal behavior, morphology and hydrophilicity of the membranes were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, element analysis, thermalgravimetric analysis, differential scanning calorimetry, scanning electron microscopy and contact angle measurements, respectively. Permeation experiments were conducted to evaluate the water flux,and the dynamic BSA fouling resistance performances were investigated, too. All the experimental results indicate that the PVDF-g-PVP membranes demonstrate better separation performances over the pristine PVDF membrane.展开更多
Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compr...Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.展开更多
基金financially supported by Natural Science Foundation of Anhui Province(Grant No.2008085QE208)the National Natural Science Foundation of China(51961165106)。
文摘Perovskite solar cells(PSCs)have become the promising next-generation photovoltaic devices due to their excellent photoelectric performances,and the power conversion efficiencies(PCEs)have experienced unprecedented rapid increase in recent years.However,to realize the practical application of PSCs,high performance and long-term stability are required and the preparation of high-quality perovskite film is the key.Herein,we adopt a simple and effective method to prepare high-quality perovskite films by introducing the poly(vinylidene fluoride)(PVDF)polymer additive with abundant hydrophobic F.As the growth template,the PVDF promotes the growth of perovskite crystal,improves the crystallinity and film morphology,thus reducing defect density and inhibiting carrier recombination.The results show that the photovoltaic performances of the perovskite device with PVDF are meaningfully improved,and a high PCE of 21.42%is achieved with an improvement of 10.87%,More importantly,the PVDF-based perovskites display greatly enhanced humidity and heat stability due to the protection of strong hydrophobic barrier from F and PVDF long chain.Aging at 45%±5%relative humidity(RH)for 2400 h and 850 C for300 h,respectively,the unsealed PVDF devices can maintain over 90%of the initial PCE.It indicates that suitable polymer additives can improve the film quality to acquire high-performance and stable PSCs and lay a foundation to design new perovskite light absorption layer with different polymers for the further development of PSCs.
基金Supported by National Natural Science Foundation of China (10875164,10805070)the Knowledge Innovation Project of Chinese Academy of Sciences,Shanghai Municipal Commission for Science and Technology (10ZR1436700),and SRF for ROCS of the Ministry of Education
文摘Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis.The degree of grafting (DG) of the grafted PVDF was determined by fluorine elemental analysis (FEA) method,and was compared with the DGs determined by weighing method,acid-base back titration method and quantitative FT-IR method.The results show that the FEA method is accurate,convenient and universal,especially for the grafted polymer powders.
基金Supported by the Shanghai Municipal Science and Technology Committee(No.08231200300)
文摘Porous membranes were prepared using the phase inversion method from poly(vinylidene fluoride)-graftpoly(N-vinyl pyrrolidone)(PVDF-g-PVP) powders, which were synthesized via γ-ray induced graft polymerization(pre-irradiation). Chemical compositions, thermal behavior, morphology and hydrophilicity of the membranes were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, element analysis, thermalgravimetric analysis, differential scanning calorimetry, scanning electron microscopy and contact angle measurements, respectively. Permeation experiments were conducted to evaluate the water flux,and the dynamic BSA fouling resistance performances were investigated, too. All the experimental results indicate that the PVDF-g-PVP membranes demonstrate better separation performances over the pristine PVDF membrane.
基金supported by the National Natural Science Foundation of China(Grant Nos.51604089,51874110,22173066,and 21903058)Natural Science Foundation of Heilongjiang Province(Grant No.YQ2021B004).
文摘Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.
