燃料电池用纳米改性聚苯并咪唑阴离子交换膜的制备

以环氧氯丙烷和1–甲基咪唑为原料制备新型离子液体(IL),以IL为原料对氧化石墨烯(GO)进行表面修饰制备离子液体功能化氧化石墨烯(IL–GO),以IL–GO为添加剂制备基于含氟聚苯并咪唑(FPBI)复合膜。研究了IL–GO的含量对复合膜的热稳定性、力学强度、离子电导率、离子交换容量(IEC)、吸水率、溶胀度和耐碱性等性能的影响。研究结果表明,复合膜的IEC、离子电导率和拉伸性能都随着IL–GO含量的增加而增大,当IL–GO含量为30%时其拉伸应力和拉伸弹性模量分别达到77.5 MPa和1.95 GPa,在80℃下,其最大离子电导率可达72.3 m S/cm,然而复合膜的热稳定性并没随着IL–GO含量的增加而改变。FPBI/IL–GO复合膜具有良好的稳定性,该系列阴离子交换膜有望在碱性阴离子交换膜燃料电池中得到应用。     

Physicochemical properties of new amide-based protic ionic liquids and their use as materials for anhydrous proton conductors

We prepared 3 protic ionic liquids based on trifluoromethanesulfonic acid and an amide, namely isobutyramide (ITSA), n-butyramide(NTSA), and benzamide(BTSA). All of the protic ionic liquids exhibit excellent thermal stability (above 200 °C). ITSA has the highest ionic conductivity, which is 32.6 mS/cm at 150 °C. ITSA was used to prepare anhydrous, conducting composite membranes based on polymers of polyvinylidene-fluoride (PVDF) to serve as intermediate temperature proton exchange membrane fuel cells. This type of composite membrane possesses good thermal stability, high ionic conductivity and good mechanical properties. Increasing the polymer content leads to the improvement of mechanical properties, but is accompanied by a reduction in ionic conductivity. We made efforts to eliminate the trade-off between strength and conductivity of the ITSA/PVDF composite membrane by adding polyamide imide, which resulted in a simultaneous increase in strength and conductivity. A conductivity of 7.5 mS/cm is achieved in a membrane containing 60 wt.% ITSA and 5 wt.% PAI in PVDF at 150 °C.     

Synthesis and characterization of poly(arylene ether sulfone)-b-polybenzimidazole copolymers for high temperature low humidity proton exchange membrane fuel cells

Multiblock copolymers based on poly(arylene ether sulfone) and polybenzimidazole (PBI) with different block lengths were synthesized by coupling carboxyl functional aromatic poly(arylene ethers) with ortho diamino functional PBI oligomers in NMP, selectively doped with phosphoric acid, and evaluated as a high temperature proton exchange membrane (PEM). Transparent and ductile membranes were produced by solvent casting from DMAc. From dynamic mechanical analysis (DMA), the neat copolymer membranes showed two distinct glass transition temperatures which implies the existence of a nanostructured morphology in the membranes. These two nanophases became more distinct with increasing block length. The membranes were immersed in various concentrations of phosphoric acid solution to produce the proton conductivity. The doping level increased with increasing concentration of the acid solution and a maximum doping level of 12 was achieved when 14.6 M phosphoric acid solution was used. The acid doped membranes showed significantly reduced swelling behavior compared to a control conventional phosphoric acid doped PBI homopolymer system which appears to be related to the selective sorption into the PBI phase. The ionic conductivity of the doped samples at 200 °C afforded up to 47 mS/cm without external humidification. The protonic conductivity was found to increase with block length at a given doping level, reflecting the sharpness of the nanophase separation and the effect was even more prominent at a low doping level of 6-7. It is suggested that the phosphoric acid doped multiblock copolymer system would be a strong candidate for high temperature and low relative humidity PEM applications such as those required for stationary power.     

聚苯并咪唑/改性聚环氧氯丙烷阴离子交换膜的性能

通过缩聚法制备了含氟聚苯并咪唑(FPBI),以1–甲基咪唑和聚环氧氯丙烷为原料,制备了咪唑盐修饰的聚环氧氯丙烷(Im PECH),并通过溶液浇铸法制备了FPBI/Im PECH复合膜。系统地研究了复合膜中Im PECH含量的不同对复合膜的力学性能、热稳定性、离子电导率、离子交换容量(IEC)、吸水率、溶胀度等性能的影响。研究结果表明,随着Im PECH含量的增加,复合膜的吸水率、溶胀度、IEC、离子电导率逐渐增加,依然能够保持良好的力学性能和热稳定性。FPBI/Im PECH复合膜在80℃下最高电导率达到55.74 m S/cm,并展示了优异的耐碱性,该复合阴离子交换膜有望在碱性阴离子交换膜燃料电池中得到应用。     

Nanostructured membranes based on sulfonated poly(aryl ether sulfone) and silica for fuel‐cell applications

Nanostructured sulfonated poly(aryl ether sulfone) (SPSU) membranes were made from SPSU/silica composites through the addition of amorphous, precipitated, and micronized silica particles (Tixosil 333) and short or segmented linear structures. Linear and branched segments of silica were obtained from the in situ reaction of tetraethoxysilane (TEOS) in an SPSU solution through a sol–gel acid‐catalyzed process. Different amounts of silica in the SPSU composites were prepared to evaluate their influence on the ionic conductivity, the water and alcohol solution sorption capacities, and the stability in an ethanol medium. The effect of silica (Tixosil) on the conductivity was higher than that of the silica made from TEOS in SPSU composites. The conductivities of the membranes containing 10% Tixosil and 6.6% silica prepared from TEOS were measured at 80°C; their values were 60 and 33 mS/cm, respectively. Furthermore, a membrane made of a silica blend (5% Tixosil and 3% TEOS) in SPSU attained a value of 92 mS/cm, whereas the commercial membrane Nafion 117, used as a reference, had a conductivity of 54 mS/cm measured under the same conditions. All those composites membranes could be used as components in hydrogen fuel cell. However, only the SPSU/2% Tixosil composite could be used in both hydrogen and ethanol direct fuel cells. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Main‐chain poly(1,2,3‐triazolium hydroxide)s obtained through AA+BB click polyaddition as anion exchange membranes

A series of aromatic poly(1,2,3‐triazolium iodide)s were synthesized by step growth polymerization of dipropargyl bisphenol A with aliphatic and aromatic diazides followed by quantitative or partial N‐alkylation of the main‐chain 1,2,3‐triazole groups using iodomethane. After characterization by ¹H NMR spectroscopy, SEC and DSC the corresponding self‐standing membranes were obtained by hot pressing. Poly(1,2,3‐triazolium iodide) membranes were converted to the corresponding hydroxide‐containing membranes by anion exchange. Structure–property correlations are discussed based on the evolution of water uptake and ionic conductivity with respect to the ionic exchange capacities of the different materials having distinct chemical structure, quaternization degree and counter‐anion structure. Poly(1,2,3‐triazolium hydroxide) anion exchange membranes exhibit water uptakes below 150% and ionic conductivity in the hydrated state up to 4 mS cm^?1 for ionic exchange capacities up to 3.2 meq g^?1. © 2019 Society of Chemical Industry     

偏氟乙烯-六氟丙烯共聚物电解质研究

以偏氟乙烯-六氟丙烯共聚物〔P(VdF-HFP)〕、LiClO4/碳酸二甲酯(DMC)/碳酸乙烯酯(EC)或LiPF6/EC/DMC/碳酸二乙酯(DEC)和纳米SiO2为原料,用自然挥发法和相转移法制成聚合物电解质膜。测试结果表明:对LiClO4/DMC/EC体系,c(LiClO4)=1mol/L,w(SiO2)=7%时,室温(21℃)电导率达最大值2 81mS/cm,72℃时达9 6mS/cm;对LiPF6/EC/DMC/DEC体系,c(LiPF6)=1mol/L,m〔P(VdF-HFP)〕∶m(SiO2)=3∶2时,室温电导率为3 68mS/cm,72℃时达13 8mS/cm。扫描电镜(SEM)和X射线衍射分析(XRD)结果表明,电解质膜为非晶态的多孔结构,纳米SiO2粉末掺入可使微孔的数目明显增多,孔隙率增加,孔分布更均匀;傅里叶红外光谱(FTIR)结果显示,P(VdF-HFP)、增塑剂与LiClO4间存在相互作用。     

Blend membranes based on sulfonated poly(ether ether ketone) and poly(vinylidene fluoride) for high performance direct methanol fuel cell

Various polymeric blends based on sulfonated poly(ether ether ketone) (sPEEK)/poly(vinylidene fluoride) (PVdF) were prepared for the membranes of direct methanol fuel cell. The blend membranes showed good compatibility within a limited composition range of less than around 10 wt% of PVdF. The blend membrane containing 2.5 wt% exhibited highest proton conductivity at room temperature among the tested blends. The dimensional stability was enhanced with introducing PVdF into the blend membrane. These could contribute to high performance of the cell based on the blend membrane.     

Tailoring solid-state synthesis routes for high confidence production of phase pure,low impedance Al-LLZO

Lithium lanthanum zirconium oxide (LLZO) garnet is a solid-state lithium ion conducting electrolyte promising all-solid-state batteries (ASSB) with high charge rates and good energy density due to its chemical stability against lithium metal anodes. LLZO has a high room temperature Li ion conductivity of ∼0.1–1 mS/cm in its cubic phase, but the stability of the cubic phase and ionic conductivity are highly sensitive to lithium stoichiometry. Stabilizing agents such as aluminum oxide and excess lithium are needed to preserve the cubic phase and compensate for lithium volatility. With the range of the end LLZO products spanning powders, porous membranes to dense membranes combined with sintering/calcination that often exceeds 1000°C, it is challenging to maintain an ideal lithium content given its high volatility from a single base powder. This study was designed to elucidate the sensitivities of aluminum doped LLZO powder synthesis and processing along its path to being utilized in a ceramic-manufacturing optimized ASSB. By utilizing thermogravimetric analysis in conjunction with in situ X-ray diffraction analysis of solid-state LLZO synthesis, it was discovered that the sensitivity of the LLZO cubic phase to lithium volatility can be reduced via early incorporation of excess lithium carbonate during initial phase formation in direct combination with controlled surface-to-volume ratios of the powders. Isostatically pressed powders of our LLZO sintered at 1100°C for 2 h showed RT ionic conductivity of 0.3–0.4 mS/cm measured via electrochemical impedance spectroscopy, and an improvement in microstructural uniformity with lowered porosity. The improved suppression of lithium volatilization has important implications for the scalable production of LLZO powders and assembly of ASSBs.     

Characterization and application of composite membranes in DMFC

The present work focuses on the characterization of membranes for direct methanol fuel cells (DMFC), prepared using composites of sulfonated poly(ether ether ketone) (sPEEK, with sulfonation degree, SD, of 42 and 68%) as polymer matrix. This polymer was inorganically modified incorporating different amounts of zirconium phosphate (ZrPh) pretreated with n-propylamine and polybenzimidazole (PBI). The investigated properties were: proton conductivity, water and aqueous methanol swelling, permeability coefficients for DMFC species and morphology. DMFC tests were performed at 110 °C with relative humidity (r.h.) in the cathode feed of 100 and 138%. The results obtained show that the inorganic modification of the polymer decreases the proton conductivity, water and aqueous methanol swelling and permeability towards DMFC species. In terms of morphology, it was found that the applied procedure enabled the preparation of membranes with good compatibility between inorganic and organic components. In terms of the DMFC tests of the composite membranes, working with the cathode feed at 100% r.h., the unmodified sPEEK membrane with SD = 42% proved to have the best performance, although with higher methanol crossover. In contrast, for r.h. of 138%, the best performance was achieved by the sPEEK composite membrane with SD = 68 and 20.0 wt.% of ZrPh and 11.2 wt.% of PBI.     

Preparation and characterization of novel chitosan‐based mixed matrix membranes resistant in alkaline media

In this work, mixed matrix membranes (MMMs) based on chitosan (CS) and different fillers (room temperature ionic liquid [emim][OAc] (IL), metallic Sn powder, layered titanosilicate AM‐4 and layered stannosilicate UZAR‐S3) were prepared by solution casting. The room temperature electrical conductivity and electrochemical response in strong alkaline medium were measured by electrochemical impedance spectroscopy and cyclic voltammetry (CV). The ionic conductivity of pure CS membranes was enhanced, from 0.070 to 0.126 mS cm^?1, for the pristine CS and Sn/CS membranes, respectively, as a function of the hydrophilic nature of the membrane and the coordination state of Sn. This hydrophilic and charge nature was corroborated by water uptake measurements, where only the introduction of IL in the CS membrane led to a water uptake of 3.96 wt %, 20 or 30 times lower than the other membranes. Good thermal and chemical stability in alkaline media were observed by thermogravimetric analyses and X‐ray photoelectron spectroscopy analyses, respectively, and good interaction between CS and the fillers observed by X‐ray diffraction, scanning electron microscopy and CV. Thus, thin CS‐based MMMs (40–139 µm), resistant in high alkaline media, show higher conductivity than pure CS membranes, especially those fillers containing tin, and although the electrochemical performance is lower than commercially available anion‐exchange membranes they have potential in pervaporation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42240.     

Ternary proton exchange membranes with low‐cost raw materials: Solvent type influence on microstructure development,high ionic conductivity,and ionic liquid lixiviation protection

A critical stage of solvent evaporation during membrane casting was identified as responsible for significant differences in performance of ternary membranes composed of PEEK with 73% of sulfonation degree. DemaTfO and MmtdemaDMF showed to be the best solvent for casting of membranes prepared through the present study, which is against the observations made through other different studies. Fractal structures are formed regardless of solvent polarity, and interlamellar spacing is found to be higher when DMF is used, which led to higher conductivity and IL leaching protection. Proton relaxometry showed that only the membranes made with DMF and DMAc possess one single mobility domain. Transmission electron microscopy micrographs showed a higher damage in membranes with two different mobility domains and consequent phase separation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46012.     

Charge Dynamics and Bending Actuation in Aquivion Membrane Swelled with Ionic Liquids

The actuation strain and speed of ionic electroactive polymer (EAP) actuators are mainly determined by the charge transport through the actuators and excess ion storage near the electrodes. We employ a recently developed theory on ion transport and storage to investigate the charge dynamics of short side chain Aquivion^® (Hyflon^®) membranes with different uptakes of ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (EMI-Tf). The results reveal the existence of a critical uptake of ionic liquids above which the membrane exhibits a high ionic conductivity (σ > 5 × 10⁻² mS/cm). Especially, we investigate the charge dynamics under voltages which are in the range for practical device operation (∼1 V and higher). The results show that the ionic conductivity, ionic mobility, and mobile ion concentration do not change with the applied voltage below 1 V (and for σ below 4 V). The results also show that bending actuation of the Aquivion membrane with 40wt% EMI-Tf is much larger than that of Nafion, indicating that the shorter flexible side chains improve the electromechanical coupling between the excess ions and the membrane backbones, while not affecting the actuation speed.     

Double crosslinked polyetheretherketone-based polymer electrolyte membranes prepared by radiation and thermal crosslinking techniques

Novel one-step preparation of polymer electrolyte membranes without a membrane casting process is achieved by radiation crosslinking of a polyetheretherketone (PEEK) film to prevent dissolution and deformation of the original film in sulfonating solutions. The films crosslinked with doses more than 33 MGy can be effectively sulfonated in a chlorosulfonic solution, resulting in a crosslinked sulfonated PEEK (sPEEK) electrolyte membrane with high proton conductivity comparable to Nafion. Nevertheless, its water uptake was high for application in fuel cells. The thermal treatment was effective for further crosslinking of the membrane; as a result, the water uptake and methanol permeability of the double crosslinked sPEEK membranes drastically decreased, compensating for a slight decrease of proton conductivity. In addition, unlike the traditional cast sPEEK membrane showing the irreversible swelling in hot water, the double crosslinked sPEEK membranes exhibited excellent stability toward 100 °C hot water for more than 200 h without any decrease in proton conductivity, and had the mechanical and thermal properties superior to those of Nafion.     

双核碱性离子液体的合成及其在阴离子交换膜中的应用

以溴代十二烷、吗啉和1,4-二溴丁烷为原料,通过两步法合成新型氢氧型N-十二烷基双核吗啉离子液体([Nbmd]OH),分别用红外光谱(FTIR)、氢核磁分析(¹H NMR)对合成的离子液体进行结构分析;采用热重(TGA)测试离子液体的热稳定性,同时测定了离子液体的溶解性和碱性.此外,以季铵化壳聚糖(QCS)为制膜原料,碱性离子液体[Nbmd]OH为掺杂物,通过溶液浇铸法制备了一系列掺杂碱性离子液体([Nbmd]OH)的交联复合膜(QCS/[Nbmd]OH).并采用FTIR、TGA、SEM对复合膜的结构、热稳定性和微观形貌进行分析,同时考察离子液体加入量对QCS/[Nbmd]OH复合膜的含水率、机械强度及导电性能等指标的影响.结果表明:随着离子液体含量的增加,QCS/[Nbmd]OH复合膜的含水率、溶胀度、电导率增加,力学性能下降.当离子液体掺杂质量分数为30%时,复合膜在70℃下的电导率为1.17×10^-2S/cm,拉伸强度为11.8 MPa,含水率和溶胀度分别为320%和236%.     

Phosphonated poly(arylene ether)s as potential high temperature proton conducting materials

The preparation and characterization of new phosphonated polymeric ionomers based on a fully aromatic poly(arylene ether) backbone with applications as proton exchange membranes for fuel cell is reported. The high-molecular-weight polymers were obtained by the polycondensation of the phosphonated monomers with decafluorobiphenyl in high yields with inherent viscosities up to 0.58 dL g⁻¹. The hydrolysis of the phosphonated ester into phosphonic acid groups was carried out quantitatively under acidic conditions. The polymers were studied by TGA after hydrolysis and showed10% weight loss above 430 °C. Membranes with total ion-exchange capacities above 6 meq/g showed proton conductivities of approximately92 mS/cm at 25 °C and 100% relative humidity increasing to ca.150 mS/cm at 140 °C. Their conductivity under dry condition showed values over 2 mS/cm at 120 °C which upon doping with phosphoric acid jumped to nearly 100 mS/cm.     

Effect of electrospinning on the ionic conductivity of polyacrylonitrile/polymethyl methacrylate nanofibrous membranes: optimization based on the response surface method

A novel fibrous polymer electrolyte membrane was produced based on polymethyl methacrylate/polyacrylonitrile (PMMA/PAN) blend. This was achieved through optimization in the loadings of the two polymers and electrospinning method. Consequently, the effect of PMMA on the ionic conductivity was assessed. A quantitative relationship between ionic conductivity and the important parameters including voltage, solution concentration, and PMMA content was determined. The response surface method (RSM) was employed to obtain the quantitative relationship and to determine the ion conductivity of PAN/PMMA electrospun membrane. Analysis of variance technique was used to study the importance of parameters and their interactions. A regression model was applied to determine the most influential factors on the ionic conductivity and to find the maximum ionic conductivity of the electrolyte membrane as an optimal result. The average fiber diameter was in the range of 206–367 nm, and the membranes were associated with high porosities between 50 and 91 %, and the electrolyte uptakes were in the range of 285–460 %. For all samples, the ionic conductivity of gel polymer electrolytes at 25 °C was above the 1 mS/cm. The ionic conductivity changed with the voltage directly and with the solution concentration inversely. According to the results, the ionic conductivity showed its dependency with the PMMA content, increasing with the PMMA content up to 50 % and smoothly decreasing with PMMA further increases. Some important interactions between the parameters were also detected.     

Study of high-temperature proton exchange membrane through one-step encapsulation of ionic liquid in sulfonated poly(ether ether ketone)

The proton exchange membrane (PEM) is the core component of a high-performance proton exchange membrane fuel cell (PEMFC). Since the traditional PEM has the disadvantages of poor cell performance and high cost, a new kind of PEM with good proton conductivity, low cost and simple preparation should be explored. In this paper, several different binary hybrid membranes were successfully prepared through one-step encapsulation of different ionic liquids (ILs) in sulfonated poly(ether ether ketone) (SPEEK). The prepared membranes were characterized by scanning electron microscope (SEM), thermogravimetric analysis (TG), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), proton conductivity measurements and dynamic mechanical analysis (DMA). SEM images showed that ILs were fully doped into SPEEK. FT-IR and XPS proved that SPEEK and IL formed a new chemical bond combined with intermolecular hydrogen bonds. The TG results showed that the binary hybrid membranes could maintain stability even at 300°C. The water uptake and swelling ratio showed that the water absorption capacity of the binary composite membrane played a vital role in improving proton conductivity. The proton conductivity study showed that ILs doping also helped to improve the proton conductivity of the SPEEK membrane. When the doping amount of IL was maintained at 30 wt.%, it has the highest proton conductivity, 25 mS cm⁻¹ at 120°C. It was proved that anhydrous hybrid membrane tetraphenyl imidazole sulfate/SPEEK ([IM2][H₂PO₄]/SPEEK) could be used in PEMFC at medium temperature.     

Mass transport of direct methanol fuel cell species in sulfonated poly(ether ether ketone) membranes

Homogeneous membranes based on sulfonated poly(ether ether ketone) (sPEEK) with different sulfonation degrees (SD) were prepared and characterized. In order to perform a critical analysis of the SD effect on the polymer barrier and mass transport properties towards direct methanol fuel cell species, proton conductivity, water/methanol pervaporation and nitrogen/oxygen/carbon dioxide pressure rise method experiments are proposed. This procedure allows the evaluation of the individual permeability coefficients in hydrated sPEEK membranes with different sulfonation degrees. Nafion^® 112 was used as reference material. DMFC tests were also performed at 50 °C. It was observed that the proton conductivity and the permeability towards water, methanol, oxygen and carbon dioxide increase with the sPEEK sulfonation degree. In contrast, the SD seems to not affect the nitrogen permeability coefficient. In terms of selectivity, it was observed that the carbon dioxide/oxygen selectivity increases with the sPEEK SD. In contrast, the nitrogen/oxygen selectivity decreases. In terms of barrier properties for preventing the DMFC reactants loss, the polymer electrolyte membrane based on the sulfonated poly(ether ether ketone) with SD lower or equal to 71%, although having slightly lower proton conductivity, presented much better characteristics for fuel cell applications compared with the well known Nafion^® 112. In terms of the DMFC tests of the studied membranes at low temperature, the sPEEK membrane with SD = 71% showed to have similar performance, or even better, as that of Nafion^® 112. However, the highest DMFC overall efficiency was achieved using sPEEK membrane with SD = 52%.     

Structure and Properties of New sPEEK/Zirconia/Protic Ionic Liquid Membranes for Fuel Cell Application

Hybrid organic–inorganic membranes based on sulfonated poly(ether ether ketone) (sPEEK), zirconium oxide, and the protic ionic liquid (PIL) diethylmethylamine triflate ([dema][T_fOH]) have been synthesized. Their structure has been investigated by X‐ray diffraction and small‐angle X‐ray scattering and correlated to their electrical and thermomechanical properties. The membranes present good mechanical and chemical stabilities, as well as thermal stability over 300 °C. Zirconia contents up to 5 wt% (10 wt% PIL) lead to the formation of isolated zirconia‐rich aggregates dispersed in the polymer matrix, constituted of spatially correlated zirconia nanoparticles. This segregation of zirconia species in nanodomains, interacting with sulfonic groups of sPEEK, inhibits conductivity. Differently, zirconia content of 6 wt% (10 wt% PIL) induces a conductivity much higher than pristine sPEEK, due to the formation of an extended fractal structure in the whole sample, constituted of connected zirconia‐rich aggregates. Interaction of PIL molecules with the zirconia aggregates along this extended structure shall form new conducting channels for ion transport, favoring conductivity.