A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place ...A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.展开更多
Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membr...Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membranes(PEMs).In this study,a series of hybrid membranes were obtained by molecular-level hybridization of Weakley-type POM Na_(7)H_(2)LaW_(10)O_(36)(LaW_(10))clusters into sulfonated poly(aryl ether ketone sulfone)(SPAEKS).All hybrid membranes exhibited greater proton conductivity than the pristine membrane in the 30–80℃temperature range.When the doping amount of LaW 10 reached 7 wt.%,the proton conductivity of M-LaW 10^(-7)achieved 64 mS·cm^(−1)at 80℃.Lanthanide ions'high coordination number property and variable coordination environment can aid to attract more water molecules from the environment.LaW 10 and these bound water can construct denser hydrogen bonds with–SO_(3)H of SPAEKS.These intensive hydrogen bonds will facilitate the constitution of more continuous proton transport channels,and improve the proton conductivity of the hybrid membrane.This work off ers a fresh approach to using POMs containing rare-earth components in PEMs.展开更多
Critical issues of Zn anodes including undesirable dendrites formation and parasitic reactions severely limit the reversibility and cyclability of Zn anodes.To address these issues,a functional Janus separator with th...Critical issues of Zn anodes including undesirable dendrites formation and parasitic reactions severely limit the reversibility and cyclability of Zn anodes.To address these issues,a functional Janus separator with the structure of a mechanically strong sulfonated poly(arylene ether sulfone)(SPAES)dense layer composited on a porous glass fiber(GF)substrate is designed.The SPAES dense layer that faces the Zn anode containing abundant sulfonic acid groups effectively promotes the desolvation process of hydrated Zn ions,guides uniform Zn ion transfer,and blocks anions and water,contributing to dendrite-free and highly reversible Zn plating/stripping cycles,while the porous GF substrate retains high electrolyte uptake.As a result,the Zn symmetric cell with the Janus separator demonstrates an ultralong cycling lifespan of over 2000 h at the areal capacity of 1 m A h cm^(-2),which is 23-fold superior to that with a pristine glass fiber separator(<90 h).More impressively,the as-prepared Janus separator enables outstanding rate performance and excellent cycling stability of full Zn ion batteries with diverse cathode materials.For instance,when paired with the V_2O_(5)cathode,the full battery with a Janus separator attains an ultrahigh initial specific capacity of 416.3 m A h g^(-1)and capacity retention of 60%over 450 cycles at 1 A g^(-1),exceeding that with a glass fiber separator.Hence,this work provides a facile yet effective approach to mitigating the dendrites formation and ameliorating the parasitic reactions of Zn metal anodes for high-performance Zn ion batteries.展开更多
A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone ...A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.展开更多
A series of comb-shaped poly(arylene ether sulfone)s containing pendant 2-methyl-3-alkylimidazolitun group(ImPAES-Cx,x=1,6,10)was prepared and characterized as novel anion exchange membranes.These Im-PAES-Cx membranes...A series of comb-shaped poly(arylene ether sulfone)s containing pendant 2-methyl-3-alkylimidazolitun group(ImPAES-Cx,x=1,6,10)was prepared and characterized as novel anion exchange membranes.These Im-PAES-Cx membranes were obtained by benzylic bromination and imidazolium functionalization.The characteristic nano-phase separation structure was formed in membranes with longer alkyl side chains,as confmned by small-angle X-ray scattering.The nano-phase separation structures endowed ImPAES-Cx membranes with improved ionic conductivity,dimensional stability(at least 60% decrease water uptake and swelling ratio at 60℃)and mechanical properties,together with excellent alkaline stability.Especially,ImPAES-C6 membranes possessed enhanced hydroxide conductivity and chemical stability simultaneously.These results suggest that it is a feasible strategy to introduce appropriate length of alkyl side chains into anion exchange membranes(AEMs)to improve the performance.展开更多
A bromine-containing poly(arylene ether sulfone) was synthesized from a(4-bromo)phenylhydroquinone monomer.A phosphonated derivative was prepared based on above brominated polymer using palladium-catalyst.Aimed at imp...A bromine-containing poly(arylene ether sulfone) was synthesized from a(4-bromo)phenylhydroquinone monomer.A phosphonated derivative was prepared based on above brominated polymer using palladium-catalyst.Aimed at improving the properties for fuel cell applications,a composite membrane was obtained by incorporating sulfonic acid-functionalized polysilsesquioxane into the phosphonated polymer through a sol-gel processing.Both phosphonated membrane and its hybrid membranes show good thermal and dimensio-nal stability.The hybrid membrane has low methanol permeability of 1.07×10-7 cm2/s and proton conducti-vity of 0.06 S/cm at 80 ℃.展开更多
基金This work was financially supported by the National Science Foundation of China (NSFC) (Key project, No. 29734120)the China High-Tech Development 863 Program (No. 2003AA302410)+1 种基金Natural Science Foundation of Guangdong Province (Excellent Team Project, No. 015007)Canton Province Sci & Tech Bureau (Key Strategic Project, No. A1100402) and Guangzhou Sci & Tech Bureau
文摘A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.
基金financially supported by the National Natural Science Foundation of China(No.22271022)the Natural Science Foundation of Jilin Province(No.YDZJ202201ZYTS342)supported by the China Scholarship Council(CSC No.201802335014).
文摘Polyoxometalates(POMs)are classified as solid superacids which can exhibit notable proton conductivity,making them a promising functional inorganic filler for enhancing the proton conductivity of proton exchange membranes(PEMs).In this study,a series of hybrid membranes were obtained by molecular-level hybridization of Weakley-type POM Na_(7)H_(2)LaW_(10)O_(36)(LaW_(10))clusters into sulfonated poly(aryl ether ketone sulfone)(SPAEKS).All hybrid membranes exhibited greater proton conductivity than the pristine membrane in the 30–80℃temperature range.When the doping amount of LaW 10 reached 7 wt.%,the proton conductivity of M-LaW 10^(-7)achieved 64 mS·cm^(−1)at 80℃.Lanthanide ions'high coordination number property and variable coordination environment can aid to attract more water molecules from the environment.LaW 10 and these bound water can construct denser hydrogen bonds with–SO_(3)H of SPAEKS.These intensive hydrogen bonds will facilitate the constitution of more continuous proton transport channels,and improve the proton conductivity of the hybrid membrane.This work off ers a fresh approach to using POMs containing rare-earth components in PEMs.
基金fully supported by the Research Grant Council Collaborative Research Fund of the Hong Kong Special Administrative Region,China (C5031-20G)。
文摘Critical issues of Zn anodes including undesirable dendrites formation and parasitic reactions severely limit the reversibility and cyclability of Zn anodes.To address these issues,a functional Janus separator with the structure of a mechanically strong sulfonated poly(arylene ether sulfone)(SPAES)dense layer composited on a porous glass fiber(GF)substrate is designed.The SPAES dense layer that faces the Zn anode containing abundant sulfonic acid groups effectively promotes the desolvation process of hydrated Zn ions,guides uniform Zn ion transfer,and blocks anions and water,contributing to dendrite-free and highly reversible Zn plating/stripping cycles,while the porous GF substrate retains high electrolyte uptake.As a result,the Zn symmetric cell with the Janus separator demonstrates an ultralong cycling lifespan of over 2000 h at the areal capacity of 1 m A h cm^(-2),which is 23-fold superior to that with a pristine glass fiber separator(<90 h).More impressively,the as-prepared Janus separator enables outstanding rate performance and excellent cycling stability of full Zn ion batteries with diverse cathode materials.For instance,when paired with the V_2O_(5)cathode,the full battery with a Janus separator attains an ultrahigh initial specific capacity of 416.3 m A h g^(-1)and capacity retention of 60%over 450 cycles at 1 A g^(-1),exceeding that with a glass fiber separator.Hence,this work provides a facile yet effective approach to mitigating the dendrites formation and ameliorating the parasitic reactions of Zn metal anodes for high-performance Zn ion batteries.
基金financially supported by the National Natural Science Foundation of China(No.21306010)。
文摘A series of multiblock sulfonated poly(arylene ether sulfone)s(SPAES)with various block lengths and predictable ion exchange capacity were synthesized from 4,4’-difluorodiphenyl sulfone,4,4’-dihydrodiphenyl sulfone and 4,4’-biphenol by one-pot and two-pot polymerization.;H-NMR and FTIR spectra confirmed the structure that sulfonic acid groups were introduced precisely on the poly(arylene ether sulfone)s by post-sulfonation which resulted in controllable sulfonation degree.The proton exchange membranes(PEMs)-based SPAES displayed excellent dimensional,thermal,antioxidant stability,proton conductivity and mechanical properties(maximum tensile stress>35 MPa).Thermogravimetric analysis indicated the prepared SPAES began to degrade above 310℃.The effects of polymerization processes,those were,one-pot hydrophobic segment process,one-pot hydrophilic segment process and two-pot process,on the properties of polymers were investigated.The proton conductivity and microphase separation of SPAES PEMs increased in order of those prepared by one-pot hydrophobic segment process,two-pot process and one-pot hydrophilic segment process.The highest conductivities of SPAES synthesized by the above processes under 80℃ and 100%relative humidity were 213(MS4),297(MB3)and 360 mS·cm^(-1)(MQ2),respectively.
基金the National Natural Science Foundation of China(No.21474036).
文摘A series of comb-shaped poly(arylene ether sulfone)s containing pendant 2-methyl-3-alkylimidazolitun group(ImPAES-Cx,x=1,6,10)was prepared and characterized as novel anion exchange membranes.These Im-PAES-Cx membranes were obtained by benzylic bromination and imidazolium functionalization.The characteristic nano-phase separation structure was formed in membranes with longer alkyl side chains,as confmned by small-angle X-ray scattering.The nano-phase separation structures endowed ImPAES-Cx membranes with improved ionic conductivity,dimensional stability(at least 60% decrease water uptake and swelling ratio at 60℃)and mechanical properties,together with excellent alkaline stability.Especially,ImPAES-C6 membranes possessed enhanced hydroxide conductivity and chemical stability simultaneously.These results suggest that it is a feasible strategy to introduce appropriate length of alkyl side chains into anion exchange membranes(AEMs)to improve the performance.
文摘A bromine-containing poly(arylene ether sulfone) was synthesized from a(4-bromo)phenylhydroquinone monomer.A phosphonated derivative was prepared based on above brominated polymer using palladium-catalyst.Aimed at improving the properties for fuel cell applications,a composite membrane was obtained by incorporating sulfonic acid-functionalized polysilsesquioxane into the phosphonated polymer through a sol-gel processing.Both phosphonated membrane and its hybrid membranes show good thermal and dimensio-nal stability.The hybrid membrane has low methanol permeability of 1.07×10-7 cm2/s and proton conducti-vity of 0.06 S/cm at 80 ℃.
