磷钨酸掺杂PVA/纳米SiO2复合膜甲醇渗透及质子导电性能的研究

研究了磷钨酸( PWA)掺杂聚乙烯醇(PVA)/纳米二氧化硅(nano SiO2)复合质子导电材料的甲醇渗透性能和质子导电性能。研究结果表明,有机无机纳米复合膜的甲醇阻隔性能随着SiO2 的加入而提高,随着PWA的加入而降低,复合膜和PVA的甲醇渗透率随甲醇浓度的增大而降低。随着温度的升高复合膜的质子导电率也相应增加,复合膜的常温质子导电率可达10-5S·cm-1。质子导电率与温度的关系不符合Arrhenius关系,可用WLF方程或VTF方程来拟合,这种复合膜的质子输送过程主要与聚合物链运动有关。纳米SiO2 的加入有利于提高复合膜在较高温度时的水保留能力,70℃时复合膜的吸水率是纯PVA吸水率的4 倍,使得复合膜可以在较高温度下使用。     

SPEEK/P4VP酸碱复合质子交换膜的制备与性能

利用4-乙烯吡啶(4-VP)碱性单体与磺化聚醚醚酮(SPEEK)共混,通过热聚合方法制备了SPEEK/P4VP酸碱复合质子交换膜,并考察了引发剂种类、用量和P4VP添加量对复合膜制备和性能的影响。质量分数为0.2%的偶氮二异丁腈较适宜作为引发剂制备复合膜;P4VP的添加使得复合膜的质子传导率和离子交换容量IEC(IEC=mmol SO3H/g drymembrane)略有下降,但复合膜的吸水率降低,抑制溶胀能力增强,且温度越高,抑制能力越为明显,此外复合膜的阻醇性能和拉伸屈服应力也有所提高,当4-VP的含量在50%(质量分数,下同)时,复合膜的甲醇渗透率与SPEEK和Nafion膜相比分别下降了70%和99%。     

PWA对SPEEK/Si02复合质子交换膜结构与性能的影响

以磺化聚醚醚酮(SPEEK)为基体,通过溶胶-凝胶法制得SPEEK/SiO<,2>/PwA复合质子交换膜,采用红外光谱、扫描电镜、交流阻抗和热重分析等方法研究了复合膜的结构与性能.结果表明,无机粒子均匀地分散在聚合物基体中,其粒径不超过70 nm.SiO<,2>与SPEEK之间的共价交联使复合膜的甲醇渗透率和溶胀度明显...     

磺化聚醚醚酮/蒙脱土复合型质子交换膜制备与性能

以磺化聚醚醚酮(SPEEK)为基体,以有机改性的蒙脱土(OMMT)为无机相,采用溶液插层法成功制备出了可望应用于直接甲醇燃料电池的SPEEK/OMMT复合型质子交换膜.通过X射线衍射(XRD)表征了复合膜的微观结构,并采用交流阻抗和隔膜扩散方法分别考察了复合膜的质子传导性能和阻醇性能.结果表明,蒙脱土的片层间距超过4.4 nm,SPEEK高分子链已插层到蒙脱土片层之间.与纯SPEEK膜相比,SPEEK/OMMT复合膜的质子传导率有所降低,但在90℃也达到了1.2×10-2S/cm的水平,而且蒙脱土的加入明显地降低了SPEEK膜的甲醇渗透率.     

新型燃料电池用质子交换膜研究进展

传统的全氟磺酸膜Nation、Dow质子交换膜、Flemion等目前在质子交换膜燃料电池中的应用最为广泛，但在高温条件下以氢或甲醇作为燃料的燃料电池中，其性能受到一定的影响，且这类膜价格昂贵，不利于推广应用，阻碍了燃料电池的商业化进程。因此，开发一种新型的价格低廉、性能良好的膜是推广应用此类电池的关键。本文简要介绍了目前各国研究的应用于高温条件下(100～160℃)质子交换膜燃料电池与直接甲醇燃料电池中的新型膜。对它们的质子传导率、甲醇渗透率等性能进行了分析比较。     

磺化聚酰亚胺/SiO2复合膜的制备及其质子交换性能研究

制备了具有不同硅含量的磺化聚酰亚胺/二氧化硅(SPI/SiO2)复合膜,研究了SiO2的引入对复合膜的力学性能、耐热性能、尺寸稳定性以及抗氧化和耐水解稳定性的影响规律,并对其质子传导率和甲醇渗透率进行了评价。结果表明,与商业化的Nafion115膜相比,复合膜表现出更优异的阻醇特性和选择透过性,其中SPI/SiO2-2复合膜具有更突出的高温质子传导特性。     

杂多酸掺杂聚酰亚胺/二氧化硅复合质子交换膜的制备和性能研究

采用溶胶-凝胶法制备了杂多酸掺杂聚酰亚胺／二氧化硅（PI／SiO2）复合质子交换膜,研究了其质子导电性能、保水能力和抗化学氧化性能。结果表明,该千态复合膜的室温质子电导率为10^-7S／cm,中温环境（100～200℃）下的电导率可达10^-5S／cm以上,随着温度和杂多酸含量的升高,其质子电导率相应升高;对膜保水性能的研究表明,SiO2和杂多酸的加入能有效提高中温条件下复合膜的保水率,少量水的参与有可能进一步提高膜的质子电导率;对膜抗氧化性的研究表明,复合膜的抗氧化能力随二氧化硅含量的增加而增加,而随杂多酸含量的增加而降低,与纯聚合物相比,该复合膜的抗氧化能力略有下降。     

PAMPS/PVA复合质子交换膜的电导率及阻醇性能

制备了聚2-丙烯酰胺-2-甲基丙磺酸(PAM PS)/聚乙烯醇(PVA)复合质子交换膜,并研究了膜的组成、甲醇水溶液浓度等对膜力学强度、电导率和甲醇渗透率的影响。实验发现,当PAM PS含量为50%时,此复合膜拉伸强度可达21.8 M Pa,电导率σ可达1.5×1-0 2S/cm,并且甲醇透过率P仅为9.8×1-0 8cm2/S。     

聚乙烯醇-聚丙烯酸共混膜的阻醇及质子导电性能研究

针对目前直接甲醇燃料电池 (DMFC)中普遍使用的Nafion系列全氟磺酸膜存在的甲醇穿透问题 ,制备了在渗透蒸发醇 -水分离领域有良好分离效果的聚乙烯醇 (PVA)和聚乙烯醇 -聚丙烯酸 (PVA -PAA)共混膜并研究了其阻醇和质子导电性能 .与Nafion1 1 7膜相比 ,PVA膜和PVA -PAA共混膜的阻醇性能有明显提高 ,其导电能力虽很大程度上依赖于外加电解质溶液 ,但PAA的混入使PVA膜材料的导电性能有了很大改善     

原位聚合法制备Nafion~/PANI复合膜及其在DMFC中的应用

用0.1mol/L(NH42)S2O8/1mol/L盐酸溶液作引发剂,采用原位化学聚合的方法将苯胺单体聚合在Nafion~112膜基体中.扫描电镜(SEM)和能谱(EDX)测试结果表明,复合膜的表面和Nafion~112膜相比有明显变化,苯胺主要聚合在膜的两侧.复合膜的红外光谱中出现明显聚苯胺(PANI)的特征吸收峰说明,苯胺成功地聚合在Nafion~112膜中.完全湿润状态下复合膜的质子电导率和Nafion~112膜相比有少许下降.甲醇渗透性能测试表明,复合膜具有明显的阻醇作用,NF/PANI-2膜的甲醇渗透率值是1.83×10-6 cm2/s和Nafion~112膜相比降低了44%.相应地由NF/PANI-2膜组装的直接甲醇燃料电池(DMFC)开路电压值比Nafion~112膜的提高了7%,最大功率密度提高了30%.     

PVA-PWA-Al2O3无机-有机复合质子交换膜的研究

以聚乙烯醇(PVA)、磷钨酸(PWA)和氧化铝(Al2O3)溶胶为原料,制备得到PVA-PWA-Al2O3无机-有机复合质子交换膜,测定了膜的电导率、含水率、溶胀度和甲醇透过系数等性质.测试结果表明,该复合膜具有较高的导电率和较好的阻醇效果,室温下测得电导率最高达到1.162 S/cm,甲醇透过系数在10-7cm2/s左右.复合膜中PWA含量增加,膜的电导率、含水率、溶胀度和甲醇透过系数都有所上升;膜中Al2O3含量增加,膜的电导率、含水率、溶胀度提高,但甲醇渗透系数稍有下降.     

DMFC用磺化聚醚醚酮/聚苯胺共混型质子交换膜的研究

磺化聚醚醚酮膜(SPEEK)是直接甲醇燃料电池(DM FC)用质子交换膜的候选材料之一,但是当温度和磺化度(D S)较高时,该膜在甲醇水溶液中溶胀非常严重,甚至溶解,其使用温度受到限制。将磺化度为50.11%的SPEEK和聚苯胺(PAN I)共混制膜,希望利用酸碱之间的相互作用对SPEEK进行改性。研究结果表明,PAN I的加入使SPEEK/PAN I共混膜的使用温度有较大提高,并且该膜还具有较高的电导率和较好的阻醇性能。     

Self‐Healing Proton‐Exchange Membranes Composed of Nafion–Poly(vinyl alcohol) Complexes for Durable Direct Methanol Fuel Cells

Proton‐exchange membranes (PEMs) that can heal mechanical damage to restore original functions are important for the fabrication of durable and reliable direct methanol fuel cells (DMFCs). The fabrication of healable PEMs that exhibit satisfactory mechanical stability, enhanced proton conductivity, and suppressed methanol permeability via hydrogen‐bonding complexation between Nafion and poly(vinyl alcohol) (PVA) followed by postmodification with 4‐carboxybenzaldehyde (CBA) molecules is presented. Compared with pure Nafion, the CBA/Nafion–PVA membranes exhibit enhanced mechanical properties with an ultimate tensile strength of ≈20.3 MPa and strain of ≈380%. The CBA/Nafion–PVA membrane shows a proton conductivity of 0.11 S cm^?1 at 80 °C, which is 1.2‐fold higher than that of a Nafion membrane. The incorporated PVA gives the CBA/Nafion–PVA membranes excellent proton conductivity and methanol resistance. The resulting CBA/Nafion–PVA membranes are capable of healing mechanical damage of several tens of micrometers in size and restoring their original proton conductivity and methanol resistance under the working conditions of DMFCs. The healing property originates from the reversibility of hydrogen‐bonding interactions between Nafion and CBA‐modified PVA and the high chain mobility of Nafion and CBA‐modified PVA.     

SPPESK/SPEEK共混质子交换膜的制备与性能

以耐溶胀性能较好的磺化聚芳醚砜酮(SPPESK)和吸水性较强的磺化聚醚醚酮(SPEEK)为原料,制备了SPPESK/SPEEK共混质子交换膜。考察了共混膜的水吸收率,水溶胀度,甲醇水溶胀度,甲醇渗透率及质子传导率和力学性能。80℃时,共混膜具有适当的水吸收(101%)和溶胀度(34%),较低的甲醇水溶胀度(20%),较高的质子传导率(0.212 S/cm),与SPPESK膜相比,质子传导率提高了18%。SPEEK的加入改善了共混膜的柔韧性,断裂拉伸应变从16.48%提高到30.43%。     

A DNA‐Threaded ZIF‐8 Membrane with High Proton Conductivity and Low Methanol Permeability

Natural biomolecules have potential as proton‐conducting materials, in which the hydrogen‐bond networks can facilitate proton transportation. Herein, a biomolecule/metal–organic framework (MOF) approach to develop hybrid proton‐conductive membranes is reported. Single‐strand DNA molecules are introduced into DNA@ZIF‐8 membranes through a solid‐confined conversion process. The DNA‐threaded ZIF‐8 membrane exhibits high proton conductivity of 3.40 × 10^?4 S cm^?1 at 25 °C and the highest one ever reported of 0.17 S cm^?1 at 75 °C, under 97% relatively humidity, attributed to the formed hydrogen‐bond networks between the DNA molecules and the water molecules inside the cavities of the ZIF‐8, but very low methanol permeability of 1.25 × 10^?8 cm² s^?1 due to the small pore entrance of the DNA@ZIF‐8 membranes. The selectivity of the DNA@ZIF‐8 membrane is thus significantly higher than that of developed proton‐exchange membranes for fuel cells. After assembling the DNA@ZIF‐8 hybrid membrane into direct methanol fuel cells, it exhibits a power density of 9.87 mW cm^?2 . This is the first MOF‐based proton‐conductivity membrane used for direct methanol fuel cells, providing bright promise for such hybrid membranes in this application.     

Synthesis and characterization of polystyrene-poly(arylene ether sulfone)-polystyrene triblock copolymer for proton exchange membrane applications

The polystyrene-poly(arylene ether sulfone)-polystyrene (PS-PAES-PS) coil-semirod-coil triblock copolymer was synthesized by the condensation reaction of PS-COCI and H2N-PAES-NH2 telechelic polymers. The reaction was facile characterized by high yields with a perfect control over the block lengths. Following a known reaction protocol it was possible to selectively sulfonate the PS block of the triblock copolymer that led to the sulfonated copolymer sPS-PAES-sPS. Studies on its proton conductivity and methanol permeability were carried out to evaluate its use as the proton exchange membrane in direct methanol fuel cells. Proton conductivity of the membranes was increased depending on the sulfonic acid group content in the sulfonated polymer. The membranes exhibited good dimensional and thermal stability, and low methanol permeability compared to Nafion 117.     

Synthesis and characterization of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) for proton exchange membranes via atom transfer radical polymerization

A series of copolymers of poly(ether sulfone ether ketone ketone) grafted poly(sulfopropyl methacrylate) (PESEKK-g-PSPMA) were successfully synthesized by atom transfer radical polymerization (ATRP) of sulfopropyl methacrylate (SPMA) after chloromethylation of poly(ether sulfone ether ketone ketone) (PESEKK) backbone. The structure of the chloromethyl PESEKK and the copolymers were carefully investigated. Variation of the polymerization time leads to the formation of copolymers with different degree of sulfonation (DS). The properties of the proton exchange membranes such as water uptake, ion exchange capacity, proton conductivity, and methanol permeability are studied with compared to those of Nafion 117 membranes and could be modulated simply by control of the ATRP time. The copolymers exhibited much lower methanol permeability and higher proton conductivity as compared with Nafion 117.     

Blend membranes from poly(2,5-benzimidazole) and poly(styrene sulfonic acid) as proton-conducting polymer electrolytes for fuel cells

Polymer electrolyte membranes were fabricated by blending of poly(2,5-benzimidazole) (ABPBI) and poly(styrene sulfonic acid) (PSSA) at several molar ratios with respect to repeating units. Fourier transform infrared spectroscopy was used to elucidate inter-polymer interactions. Surface morphology was studied through scanning electron microscope. Thermal properties of the membranes were investigated by thermogravimetric analysis and differential scanning calorimetry. The spectroscopic measurements and water uptake (WU) studies indicate a complexation between ABPBI and PSSA where the swelling behavior of membranes increases with the PSSA content. Proton conductivities of the anhydrous and humidified samples were measured using impedance spectroscopy. Proton conductivity of ABPBI:PSSA bend with (1:4) molar ratio was detected as around 10⁻³ S/cm at higher temperatures under anhydrous conditions. On the other hand, the membrane ABPBI:PSSA (1:2) showed the proton conductivity of 0.02 S/cm (ambient temperature, RH = 50%) which is at least five-order of magnitude higher than the anhydrous material.