Sustainable energy technologies,particularly fuel cells,are gaining attraction for their potential to reduce carbon emissions and provide efficient power.Proton exchange membrane fuel cells(PEMFCs)have been central to...Sustainable energy technologies,particularly fuel cells,are gaining attraction for their potential to reduce carbon emissions and provide efficient power.Proton exchange membrane fuel cells(PEMFCs)have been central to this development.However,one persistent issue with lowtemperature PEMFCs is the dehydration of Nafion ionomer at elevated temperatures,which severely limits proton conductivity.Wang et al.tackle this by introducing a covalent organic framework(COF)interwoven with Nafion,addressing the challenge of maintaining proton conductivity and oxygen transport in medium temperatures(100–120℃).展开更多
CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient...CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.展开更多
With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate...With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.展开更多
As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper...As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.展开更多
The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing...The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.展开更多
Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with P...Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with PEMFCs owing to the more challenging water management,which severely hinders its development and real-life applications.In this study,we introduce the strategy to boost the performance and stability of the membrane electrode assembly(MEA)of AEMFCs by regulating the hydrophilicity of the anode and cathode ionomers.Two poly(biphenyl alkylene)ionomers with different hydrophilicity are synthesized and used to fabricate MEAs with asymmetric or symmetric ionomer configurations in the anodic and cathodic catalyst layers(CLs)for AEMFCs.Molecular dynamics(MD)simulations have revealed different diffusion rates of water in the hydrophobic anode and the hydrophilic cathode,which show the potential of this design to improve water management in AEMFCs,The effectiveness of this design is also confirmed by experimental results that the MEA with this asymmetric configuration exhibits the highest power and current densities of 1.58 W cm^(-2)or 5.58 A cm^(-2),respectively,among all configurations.Furthermore,this configuration also enhances the durability,with the MEA showing a voltage decay rate of only 313.1μV h^(-1)after 500 h of in-situ durability test at 0.2 A cm^(-2).This study provides new insights into the rational design of more efficient water management in MEA for high-performance AEMFCs.展开更多
Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte los...Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.展开更多
Owing to its high production volume and wide range of application s,polyethylene has gained a great deal of attention,but its low surface energy and non-polar nature have limited its application in some important fiel...Owing to its high production volume and wide range of application s,polyethylene has gained a great deal of attention,but its low surface energy and non-polar nature have limited its application in some important fields.In this study,ethylene/11-iodo-1-undecene copolymers were prepared and used as the intermediates to afford a series of imidazolium-based ionomers bearing methanesulfonate(CH_(3)SO_(3)^(-)),trifluoromethanesulfonate(CF_(3)SO_(3)^(-)),or bis(trifluoromethane)sulfonimide(Tf_(2)N^(-))counteranions.The tensile test results showed that the stress-at-break(7.8-25.6 MPa)and the elongation-at-break(445%-847%)of the ionomers could be adjusted by changing the counterion species and the ionic group contents.Most importantly,the ionomers exhibited marvelous antibacterial activities against Staphylococcus aureus(S.aureus)and Escherichia coli(E.coli).The ionomers bearing Tf_(2)N^(-)exhibited antibacterial activities>99%against both S.aureus and E.coli when ionic content reached 9.1%.The imidazolium-based ionomers prepared in this work demonstrated excellent comprehensive properties,especially highefficient and broad-spectrum antibacterial ability,exhibiting the potential fo r the application as the antibacterial materials in packaging,medical,and other fields.展开更多
In this study,we prepared unentangled and slightly entangled poly(L-lactic acid)telechelic ionomer samples(Mn=5 and 16 kg/mol)based on sodium sulfonate groups.The telechelic samples exhibit extremely slow crystallizat...In this study,we prepared unentangled and slightly entangled poly(L-lactic acid)telechelic ionomer samples(Mn=5 and 16 kg/mol)based on sodium sulfonate groups.The telechelic samples exhibit extremely slow crystallization kinetics below the melting temperature T_(m) and above the glass transition temperature T_(g),which enables us to examine the linear viscoelasticity of the ionomer melt samples therein.The application of either the shear flow(at 85℃)or elongational flow(between 70 and 90℃)strongly accelerates the crystallization,leading to strong strain hardening and formation of highly orientedαcrystals.Depending on the relative average rates of the strain-induced dissociation and strain-induced crystallization,the stress evolution can be classified into two cases,and the critical work for strain-induced crystallization is higher in case where the strain-induced dissociation occurs earlier than the strain-induced crystallization.展开更多
Imidazolium-based elastomeric ionomers （i-BIIR） were facilely synthesized by ionically modified brominated poly（isobutylene-co-isoprene） （BIIR） with different alkyl chain imidazole and thoroughly explored as nov...Imidazolium-based elastomeric ionomers （i-BIIR） were facilely synthesized by ionically modified brominated poly（isobutylene-co-isoprene） （BIIR） with different alkyl chain imidazole and thoroughly explored as novel toughening agents for poly（lactic acid） （PLA）. The miscibility, thermal behavior, phase morphology and mechanical property of ionomers and blends were investigated through dynamic mechanical analyses （DMA）, differential scanning calorimetry （DSC）, scanning electron microscopy （SEM）, tensile and impact testing. DMA and SEM results showed that better compatibility between the PLA and i-BIIR was achieved compared to the PLA/unmodified BIIR elastomer. A remarkable improvement in ductility with an optimum elongation at break up to 235% was achieved for the PLA/i-BIIR blends with 1-dodecylimidazole alkyl chain （i-BIIR-12）, more than 10 times higher than that of pure PLA. The impact strengths of PLA were enhanced from 1.9 kJ/m2 to 4.1 k J/m2 for the PLA/10 wt% i-BIIR-12 blend. Toughening mechanism had been established by systematical analysis of the compatibility, intermolecular interaction and phase structures of the blends. Interracial cavitations initiated massive shear yielding of the PLA matrix owing to a suitable interfacial adhesion which played a key role in the enormous toughening effect in these blends. We believed that introducing imidazolium group into the BIIR elastomer was vital for the formation of a suitable interfacial adhesion.展开更多
SMPU （shape memory polyurethane） non-ionomers and ionomers, synthesized with poly（c-caprolactone） （PCL）, 4, 4＇-diphenylmethane diisocyanate （MDI）, 1,4-butanediol （BDO）, dimethylolpropionic acid （DMPA） wer...SMPU （shape memory polyurethane） non-ionomers and ionomers, synthesized with poly（c-caprolactone） （PCL）, 4, 4＇-diphenylmethane diisocyanate （MDI）, 1,4-butanediol （BDO）, dimethylolpropionic acid （DMPA） were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content.展开更多
A side-chain liquid crystalline ionomer（SLCI） was synthesized by grafting copolymerization of 4-（4-ethoxybenzoyloxy）-4＇-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blend...A side-chain liquid crystalline ionomer（SLCI） was synthesized by grafting copolymerization of 4-（4-ethoxybenzoyloxy）-4＇-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blended with polypropylene（PP） and polybutylene terephthalate（PBT） by melt mixing. The thermal behavior, liquid crystalline properties, morphological structure, and mechanical properties of the blends were investigated by differential scanning calorimetry（DSC）, polarizing optical microscopy（POM）, scanning electron microscopy（SEM）, and tensile measurement. When a proper amount of SLCI was added, fine configurations were formed in the PBT/PP/SLCI blend system, and the mechanical properties were improved due to improved adhesion at the interface. When excess SLCI was added, an inhomogeneous structure resulted, which caused the mechanical properties to deteriorate.展开更多
Regardless of the excellent properties of glass ionomer cements,their poor mechanical properties limit their applications to non-load bearing areas.This study aimed to investigate the effect of incorporated short,chop...Regardless of the excellent properties of glass ionomer cements,their poor mechanical properties limit their applications to non-load bearing areas.This study aimed to investigate the effect of incorporated short,chopped and randomly distributed flax fibers（0,0.5,1,2.5,5 and 25 wt%） on setting reaction kinetics,and mechanical and morphological properties of glass ionomer cements.Addition of flax fibers did not significantly affect the setting reaction extent.According to their content,flax fibers increased the compressive（from 148 to 250 MPa） and flexure strength（from 20 to 42 MPa）.They also changed the brittle behavior of glass ionomer cements to a plastic one.They significantly reduced the compressive（from 3 to 1.3 GPa） and flexure modulus（from 19 to 14 GPa）.Accordingly,flax fiber-modified glass ionomer cements could be potentially used in high-stress bearing areas.展开更多
Objective:This study deals with the effect of phosphoric acid etching and conditioning on enamel micro-tensile bond strengths(μTBSs)of conventional and resin-modified glass ionomer cements(GICs/RMGICs).Methods:Forty-...Objective:This study deals with the effect of phosphoric acid etching and conditioning on enamel micro-tensile bond strengths(μTBSs)of conventional and resin-modified glass ionomer cements(GICs/RMGICs).Methods:Forty-eight bovine incisors were prepared into rectangular blocks.Highly-polished labial enamel surfaces were either acid-etched,conditioned with liquids of cements,or not further treated(control).Subsequently,two matching pre-treated enamel surfaces were cemented together with one of four cements[two GICs:Fuji I(GC),Ketac Cem Easymix(3M ESPE);two RMGICs:Fuji Plus(GC),RelyX Luting(3M ESPE)]in preparation forμTBS tests.Pre-treated enamel surfaces and cement-enamel interfaces were analyzed by scanning electron microscopy(SEM).Results:Phosphoric acid etching significantly increased the enamelμTBS of GICs/RMGICs.Conditioning with the liquids of the cements produced significantly weaker or equivalent enamelμTBS compared to the control.Regardless of etching,RMGICs yielded stronger enamelμTBS than GICs.A visible hybrid layer was found at certain enamelcement interfaces of the etched enamels.Conclusions:Phosphoric acid etching significantly increased the enamelμTBSs of GICs/RMGICs.Phosphoric acid etching should be recommended to etch the enamel margins before the cementation of the prostheses such as inlays and onlays,using GICs/RMGICs to improve the bond strengths.RMGICs provided stronger enamel bond strength than GICs and conditioning did not increase enamel bond strength.展开更多
A series of novel polysiloxane polyurea-urethane blockcopolymers based on methylene bis(p-phenylisocyanate (MDI), sodium-s-1,2-dihydroxy propyl sulphonate (SDPS) and aminopropyl-terminated polydimethylsiloxane (ATPS) ...A series of novel polysiloxane polyurea-urethane blockcopolymers based on methylene bis(p-phenylisocyanate (MDI), sodium-s-1,2-dihydroxy propyl sulphonate (SDPS) and aminopropyl-terminated polydimethylsiloxane (ATPS) was synthesized with varying length of soft segments and neutralizing cation. The effect of the chemical composition and the cation on the morphology and mechanical properties of the samples were studied. It was found that the SDPS chain extender based samples have definite chemical structure (-MDI-SDPS-MDI-ATPS-). As the length of the soft segment increases, an improvement of phase separation was observed. In addition, when SO3Na was translated into SO3H or the sulphonic acid groups were neutralized with different charge cations (Na+, Zn2+ and Al3+), the morphology and mechanical properties changed greatly.展开更多
As an alternative to conventional encapsulation concepts for a double glass photovoltaic(PV)module,we introduce an innovative ionomer-based multi-layer encapsulant,by which the application of additional edge sealing t...As an alternative to conventional encapsulation concepts for a double glass photovoltaic(PV)module,we introduce an innovative ionomer-based multi-layer encapsulant,by which the application of additional edge sealing to prevent moisture penetration is not required.The spontaneous moisture absorption and desorption of this encapsulant and its raw materials,poly(ethylene-co-acrylic acid)and an ionomer,are analyzed under different climatic conditions in this work.The relative air humidity is thermodynamically the driving force for these inverse processes and determines the corresponding equilibrium moisture content(EMC).Higher air humidity results in a larger EMC.The homogenization of the absorbed water molecules is a diffusion-controlled process,in which temperature plays a dominant role.Nevertheless,the diffusion coefficient at a higher temperature is still relatively low.Hence,under normal climatic conditions for the application of PV modules,we believe that the investigated ionomer-based encapsulant can“breathe”the humidity:During the day,when there is higher relative humidity,it“inhales”(absorbs)moisture and restrains it within the outer edge of the module;then at night,when there is a lower relative humidity,it“exhales”(desorbs)the moisture.In this way,the encapsulant protects the cell from moisture ingress.展开更多
The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structu...The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point,and HDT of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).The effect of Zn-SEPDM on the compatibility the morphology and properties of IPP blends were studied by DSC, TEM and mechanical properties test. The results show that as Zn-SEPDM content exceeds 20%. Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred there from. Owing to the incorporation of ionic groups into EPDM.the strong interactions betWeen the chains make both the impact and the tensile strength of IPP remarkably higher展开更多
Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ...Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.展开更多
Poly（methyl methacrylate） （PMMA） based ionomers with different lanthanum （La（III）） contents （PMMA-XLa） synthesized by free radical solution polymerization were applied to poly（vinyl chloride） （PVC） resin...Poly（methyl methacrylate） （PMMA） based ionomers with different lanthanum （La（III）） contents （PMMA-XLa） synthesized by free radical solution polymerization were applied to poly（vinyl chloride） （PVC） resins as a kind of multifunctional aids, and their performances were evaluated by measuring the static stability time, initial discoloration, transparency, fusion behavior and tensile strength of the modified PVC. The ionomers with proper lanthanum （La（III）） contents show a better thermal stability efficiency in comparison with traditional stabilizer lanthanum stearate. Meantime, they can accelerate PVC plasticization more efficiently than PMMA. The rigid PVC products stabilized with the ionomers present good transparency and enhanced tensile strength.展开更多
The electrode ionomer plays a crucial role in the catalyst layer(CL) of a proton-exchange membrane fuel cell(PEMFC) and is closely associated with the proton conduction and gas transport properties,structural stabilit...The electrode ionomer plays a crucial role in the catalyst layer(CL) of a proton-exchange membrane fuel cell(PEMFC) and is closely associated with the proton conduction and gas transport properties,structural stability,and water management capability.In this review,we discuss the CL structural characteristics and highlight the latest advancements in ionomer material research.Additionally,we comprehensively introduce the design concepts and exceptional performances of porous electrode ionomers,elaborate on their structural properties and functions within the fuel cell CL,and investigate their effect on the CL microstructure and performance.Finally,we present a prospective evaluation of the developments in the electrode ionomer for fabricating CL,offering valuable insights for designing and synthesizing more efficient electrode ionomer materials.By addressing these facets,this review contributes to a comprehensive understanding of the role and potential of electrode ionomers for enhancing PEMFC performance.展开更多
基金financial support from the National Natural Science Foundation of China(No.22301139)the Natural Science Foundation of Jiangsu Province(No.BK 20230375).
文摘Sustainable energy technologies,particularly fuel cells,are gaining attraction for their potential to reduce carbon emissions and provide efficient power.Proton exchange membrane fuel cells(PEMFCs)have been central to this development.However,one persistent issue with lowtemperature PEMFCs is the dehydration of Nafion ionomer at elevated temperatures,which severely limits proton conductivity.Wang et al.tackle this by introducing a covalent organic framework(COF)interwoven with Nafion,addressing the challenge of maintaining proton conductivity and oxygen transport in medium temperatures(100–120℃).
基金National Key R&D Program of China(2023YFA1507902,2021YFA1500804)the National Natural Science Foundation of China(22121004,22038009,22250008)+2 种基金the Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107)the Program of Introducing Talents of Discipline to Universities,China(No.BP0618007)the Xplorer Prize,China,for their financial support。
文摘CO_(2)reduction reaction(CO_(2)RR)electrolyzers based on gas diffusion electrode(GDE)enable the direct mass transfer of CO_(2)to the catalyst surface for participation in the reaction,thereby establishing an efficient three-phase reaction interface that significantly enhances current density.However,current hydrophobic modification methods face difficulties in achieving precise and substantial control over wettability,and the hydrophobic modifiers tend to significantly impair the conductivity of the electrode and ion transport capabilities.This study employs Nafion ionomers to hydrophobically modify the threedimensional catalyst layer,revealing the bifunctionality of Nafion.The fluorinated backbone of Nafion ensures the hydrophobicity of the entire catalyst layer,while its sulfonic acid groups promote ion transport,without significantly affecting the conductivity of the electrode.Furthermore,by employing modifiers with distinct wettability characteristics,a highly efficient and large-scale manipulation of the hydrophilic/hydrophobic properties of the catalyst layer was successfully realized.The electrode,constructed with silver nanopowder as a representative catalyst and modified with the hydrophobic ionomer Nafion,exhibits a substantial enhancement in both catalytic activity and durability.The optimized electrode exhibited exceptional electrocatalytic performance in both flow cell and membrane electrode assembly(MEA)configurations.Notably,in the MEA,the electrode achieved a remarkable CO Faradaic efficiency(FE)of 93.3%at a total current density of 200 mA cm^(-2),while maintaining stable operation for over 62 h.
基金supported by the National Natural Science Foundation of China(No.52394204)by the Shanghai Municipal Science and Technology Major Project。
文摘With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.
基金Project(52271013)supported by the National Natural Science Foundation of ChinaProject(23DZ1200600)supported by the Science and Technology Innovation Action Plan of Shanghai,China。
文摘As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.
文摘The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.
基金supported by the National Key R&D Program of China(No.2023YFB4004700)。
文摘Anion exchange membrane fuel cells(AEMFCs)are considered a more affordable technology compared to proton exchange membrane fuel cells(PEMFCs),but the performance and durability of AEMFCs are still not competent with PEMFCs owing to the more challenging water management,which severely hinders its development and real-life applications.In this study,we introduce the strategy to boost the performance and stability of the membrane electrode assembly(MEA)of AEMFCs by regulating the hydrophilicity of the anode and cathode ionomers.Two poly(biphenyl alkylene)ionomers with different hydrophilicity are synthesized and used to fabricate MEAs with asymmetric or symmetric ionomer configurations in the anodic and cathodic catalyst layers(CLs)for AEMFCs.Molecular dynamics(MD)simulations have revealed different diffusion rates of water in the hydrophobic anode and the hydrophilic cathode,which show the potential of this design to improve water management in AEMFCs,The effectiveness of this design is also confirmed by experimental results that the MEA with this asymmetric configuration exhibits the highest power and current densities of 1.58 W cm^(-2)or 5.58 A cm^(-2),respectively,among all configurations.Furthermore,this configuration also enhances the durability,with the MEA showing a voltage decay rate of only 313.1μV h^(-1)after 500 h of in-situ durability test at 0.2 A cm^(-2).This study provides new insights into the rational design of more efficient water management in MEA for high-performance AEMFCs.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22179130,22379143,22479145)。
文摘Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.
基金financially supported by the National Natural Science Foundation of China(No.52130307)。
文摘Owing to its high production volume and wide range of application s,polyethylene has gained a great deal of attention,but its low surface energy and non-polar nature have limited its application in some important fields.In this study,ethylene/11-iodo-1-undecene copolymers were prepared and used as the intermediates to afford a series of imidazolium-based ionomers bearing methanesulfonate(CH_(3)SO_(3)^(-)),trifluoromethanesulfonate(CF_(3)SO_(3)^(-)),or bis(trifluoromethane)sulfonimide(Tf_(2)N^(-))counteranions.The tensile test results showed that the stress-at-break(7.8-25.6 MPa)and the elongation-at-break(445%-847%)of the ionomers could be adjusted by changing the counterion species and the ionic group contents.Most importantly,the ionomers exhibited marvelous antibacterial activities against Staphylococcus aureus(S.aureus)and Escherichia coli(E.coli).The ionomers bearing Tf_(2)N^(-)exhibited antibacterial activities>99%against both S.aureus and E.coli when ionic content reached 9.1%.The imidazolium-based ionomers prepared in this work demonstrated excellent comprehensive properties,especially highefficient and broad-spectrum antibacterial ability,exhibiting the potential fo r the application as the antibacterial materials in packaging,medical,and other fields.
基金This work was financially supported by the National Natural Science Foundation of China(No.22173095).
文摘In this study,we prepared unentangled and slightly entangled poly(L-lactic acid)telechelic ionomer samples(Mn=5 and 16 kg/mol)based on sodium sulfonate groups.The telechelic samples exhibit extremely slow crystallization kinetics below the melting temperature T_(m) and above the glass transition temperature T_(g),which enables us to examine the linear viscoelasticity of the ionomer melt samples therein.The application of either the shear flow(at 85℃)or elongational flow(between 70 and 90℃)strongly accelerates the crystallization,leading to strong strain hardening and formation of highly orientedαcrystals.Depending on the relative average rates of the strain-induced dissociation and strain-induced crystallization,the stress evolution can be classified into two cases,and the critical work for strain-induced crystallization is higher in case where the strain-induced dissociation occurs earlier than the strain-induced crystallization.
基金financially support by the National Natural Science Foundation of China (No. 51573130)
文摘Imidazolium-based elastomeric ionomers （i-BIIR） were facilely synthesized by ionically modified brominated poly（isobutylene-co-isoprene） （BIIR） with different alkyl chain imidazole and thoroughly explored as novel toughening agents for poly（lactic acid） （PLA）. The miscibility, thermal behavior, phase morphology and mechanical property of ionomers and blends were investigated through dynamic mechanical analyses （DMA）, differential scanning calorimetry （DSC）, scanning electron microscopy （SEM）, tensile and impact testing. DMA and SEM results showed that better compatibility between the PLA and i-BIIR was achieved compared to the PLA/unmodified BIIR elastomer. A remarkable improvement in ductility with an optimum elongation at break up to 235% was achieved for the PLA/i-BIIR blends with 1-dodecylimidazole alkyl chain （i-BIIR-12）, more than 10 times higher than that of pure PLA. The impact strengths of PLA were enhanced from 1.9 kJ/m2 to 4.1 k J/m2 for the PLA/10 wt% i-BIIR-12 blend. Toughening mechanism had been established by systematical analysis of the compatibility, intermolecular interaction and phase structures of the blends. Interracial cavitations initiated massive shear yielding of the PLA matrix owing to a suitable interfacial adhesion which played a key role in the enormous toughening effect in these blends. We believed that introducing imidazolium group into the BIIR elastomer was vital for the formation of a suitable interfacial adhesion.
基金This work was supported by Hong Kong ITF research project (No. ITS 098/02).
文摘SMPU （shape memory polyurethane） non-ionomers and ionomers, synthesized with poly（c-caprolactone） （PCL）, 4, 4＇-diphenylmethane diisocyanate （MDI）, 1,4-butanediol （BDO）, dimethylolpropionic acid （DMPA） were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content.
基金Supported by the National Natural Science Foundation of China(No50673105)
文摘A side-chain liquid crystalline ionomer（SLCI） was synthesized by grafting copolymerization of 4-（4-ethoxybenzoyloxy）-4＇-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blended with polypropylene（PP） and polybutylene terephthalate（PBT） by melt mixing. The thermal behavior, liquid crystalline properties, morphological structure, and mechanical properties of the blends were investigated by differential scanning calorimetry（DSC）, polarizing optical microscopy（POM）, scanning electron microscopy（SEM）, and tensile measurement. When a proper amount of SLCI was added, fine configurations were formed in the PBT/PP/SLCI blend system, and the mechanical properties were improved due to improved adhesion at the interface. When excess SLCI was added, an inhomogeneous structure resulted, which caused the mechanical properties to deteriorate.
文摘Regardless of the excellent properties of glass ionomer cements,their poor mechanical properties limit their applications to non-load bearing areas.This study aimed to investigate the effect of incorporated short,chopped and randomly distributed flax fibers（0,0.5,1,2.5,5 and 25 wt%） on setting reaction kinetics,and mechanical and morphological properties of glass ionomer cements.Addition of flax fibers did not significantly affect the setting reaction extent.According to their content,flax fibers increased the compressive（from 148 to 250 MPa） and flexure strength（from 20 to 42 MPa）.They also changed the brittle behavior of glass ionomer cements to a plastic one.They significantly reduced the compressive（from 3 to 1.3 GPa） and flexure modulus（from 19 to 14 GPa）.Accordingly,flax fiber-modified glass ionomer cements could be potentially used in high-stress bearing areas.
基金Project supported by the National Natural Science Foundation of China(No.20973152)the Zhejiang Provincial Natural Science Foundation of China(No.Y2080045)
文摘Objective:This study deals with the effect of phosphoric acid etching and conditioning on enamel micro-tensile bond strengths(μTBSs)of conventional and resin-modified glass ionomer cements(GICs/RMGICs).Methods:Forty-eight bovine incisors were prepared into rectangular blocks.Highly-polished labial enamel surfaces were either acid-etched,conditioned with liquids of cements,or not further treated(control).Subsequently,two matching pre-treated enamel surfaces were cemented together with one of four cements[two GICs:Fuji I(GC),Ketac Cem Easymix(3M ESPE);two RMGICs:Fuji Plus(GC),RelyX Luting(3M ESPE)]in preparation forμTBS tests.Pre-treated enamel surfaces and cement-enamel interfaces were analyzed by scanning electron microscopy(SEM).Results:Phosphoric acid etching significantly increased the enamelμTBS of GICs/RMGICs.Conditioning with the liquids of the cements produced significantly weaker or equivalent enamelμTBS compared to the control.Regardless of etching,RMGICs yielded stronger enamelμTBS than GICs.A visible hybrid layer was found at certain enamelcement interfaces of the etched enamels.Conclusions:Phosphoric acid etching significantly increased the enamelμTBSs of GICs/RMGICs.Phosphoric acid etching should be recommended to etch the enamel margins before the cementation of the prostheses such as inlays and onlays,using GICs/RMGICs to improve the bond strengths.RMGICs provided stronger enamel bond strength than GICs and conditioning did not increase enamel bond strength.
文摘A series of novel polysiloxane polyurea-urethane blockcopolymers based on methylene bis(p-phenylisocyanate (MDI), sodium-s-1,2-dihydroxy propyl sulphonate (SDPS) and aminopropyl-terminated polydimethylsiloxane (ATPS) was synthesized with varying length of soft segments and neutralizing cation. The effect of the chemical composition and the cation on the morphology and mechanical properties of the samples were studied. It was found that the SDPS chain extender based samples have definite chemical structure (-MDI-SDPS-MDI-ATPS-). As the length of the soft segment increases, an improvement of phase separation was observed. In addition, when SO3Na was translated into SO3H or the sulphonic acid groups were neutralized with different charge cations (Na+, Zn2+ and Al3+), the morphology and mechanical properties changed greatly.
文摘As an alternative to conventional encapsulation concepts for a double glass photovoltaic(PV)module,we introduce an innovative ionomer-based multi-layer encapsulant,by which the application of additional edge sealing to prevent moisture penetration is not required.The spontaneous moisture absorption and desorption of this encapsulant and its raw materials,poly(ethylene-co-acrylic acid)and an ionomer,are analyzed under different climatic conditions in this work.The relative air humidity is thermodynamically the driving force for these inverse processes and determines the corresponding equilibrium moisture content(EMC).Higher air humidity results in a larger EMC.The homogenization of the absorbed water molecules is a diffusion-controlled process,in which temperature plays a dominant role.Nevertheless,the diffusion coefficient at a higher temperature is still relatively low.Hence,under normal climatic conditions for the application of PV modules,we believe that the investigated ionomer-based encapsulant can“breathe”the humidity:During the day,when there is higher relative humidity,it“inhales”(absorbs)moisture and restrains it within the outer edge of the module;then at night,when there is a lower relative humidity,it“exhales”(desorbs)the moisture.In this way,the encapsulant protects the cell from moisture ingress.
文摘The morphology and properties of HDPE blends with Zn-SEPDM and GR were studied through SEM and mechanical property test. The results show that as Zn-SEPDM/GR content amounts to 20%, the blend becomes an IPN in structure, and that a rather high impact and tensile strength of HDPE may be obtained after blending. The antistatic effect, the softening point,and HDT of the blend are higher as compared to HDPE/Zn-SEPDM/ZnSt (zinc stearate).The effect of Zn-SEPDM on the compatibility the morphology and properties of IPP blends were studied by DSC, TEM and mechanical properties test. The results show that as Zn-SEPDM content exceeds 20%. Zn-SEPDM in the blend becomes continuous and an abrupt change in impact strength is incurred there from. Owing to the incorporation of ionic groups into EPDM.the strong interactions betWeen the chains make both the impact and the tensile strength of IPP remarkably higher
文摘Sulfonated syndiotactic polystyrene ionomers (SsPS) with 1.8 mol% degree of sulfonation have been studied. WAXD shows that the crystallinity of SsPS ionomers was decreased with increasing diameter size of the counter ions and sPS > SsPS-H > SsPS-K > SsPS-Zn. Moreover, SsPS ionomers only have alpha crystal form, while original sPS has two crystal forms: alpha and beta crystal form. TGA shows that the thermal stability of SsPS ionomers is higher than that of the original sPS and SsPS-Zn > SsPS-K > SsPS-H. DSC shows that all the glass transition temperatures (T-g) of SsPS ionomers are higher than that of the neat sPS and SsPS-Zn > SsPS-Na > SsPS-K > SsPS-H. However, the melting temperature (T-m) and crystallization peak temperature (T-p) of SsPS ionomers are lower and SsPS-H > SsPS-Zn > SsPS-K > SsPS-Na, while the crystallinity (X-c) of SsPS-Zn is the lowest. Nonisothermal crystallization kinetics shows that the Avrami index of sPS and SsPS-H are both about 4, suggesting the nucleation growth of SsPS-H with lower degree of sulfonation still keeps its three-dimension form. FTIR spectra of SsPS ionomers show a splitting absorption band for asymmetric stretching vibration of sulfonation group. The CH in-plane bending vibration of benzene ring shifted to higher wavenumber and the symmetric stretching vibration of sulfonation group changed slightly with different counter ion neutralized SsPS ionomers.
文摘Poly（methyl methacrylate） （PMMA） based ionomers with different lanthanum （La（III）） contents （PMMA-XLa） synthesized by free radical solution polymerization were applied to poly（vinyl chloride） （PVC） resins as a kind of multifunctional aids, and their performances were evaluated by measuring the static stability time, initial discoloration, transparency, fusion behavior and tensile strength of the modified PVC. The ionomers with proper lanthanum （La（III）） contents show a better thermal stability efficiency in comparison with traditional stabilizer lanthanum stearate. Meantime, they can accelerate PVC plasticization more efficiently than PMMA. The rigid PVC products stabilized with the ionomers present good transparency and enhanced tensile strength.
基金supported by the National Natu-ral Science Foundation of China(Nos.21625102,21971017,and 22102008)National Key Research and Development Program of China(No.2020YFB1506300)Postdoctoral Fund of China(Nos.2020T130055 and 2020M670143).
文摘The electrode ionomer plays a crucial role in the catalyst layer(CL) of a proton-exchange membrane fuel cell(PEMFC) and is closely associated with the proton conduction and gas transport properties,structural stability,and water management capability.In this review,we discuss the CL structural characteristics and highlight the latest advancements in ionomer material research.Additionally,we comprehensively introduce the design concepts and exceptional performances of porous electrode ionomers,elaborate on their structural properties and functions within the fuel cell CL,and investigate their effect on the CL microstructure and performance.Finally,we present a prospective evaluation of the developments in the electrode ionomer for fabricating CL,offering valuable insights for designing and synthesizing more efficient electrode ionomer materials.By addressing these facets,this review contributes to a comprehensive understanding of the role and potential of electrode ionomers for enhancing PEMFC performance.
