溶胶—凝胶法制备磷酸掺杂聚苯并咪唑质子交换膜研究
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摘要
聚苯并咪唑(PBI)由于其突出的热稳定性,可被用做高温质子交换膜燃料电池的膜电解质材料。纯PBI膜在室温下的电导率仅为10-7S/cm,通过浸泡磷酸使其质子化是一种常用的提高其电导率的方法。通常采用溶液浇注法制备纯PBI膜,但由于PBl分子的刚性结构其难溶解在有机溶剂中,尤其对于聚合度较大的PBI聚合物。PBI聚合物在有机溶剂中的溶解难题给进一步开发PBI类质子交换膜带来困难。为此研究者提出利用三氟乙酸与磷酸混合酸作为溶剂溶解PBI再直接浇注成膜的办法；也有研究者提出通过修饰PBl分子骨架结构,如在分子骨架中引入醚键、六氟双苯丙基、侧链烷基等的办法降低分子刚性,从而改善其在有机溶剂中的溶解性。但这些办法在改善PBI溶解性的同时,往往增加了制膜成本,或以牺牲PBI原有分子骨架结构为代价。
本文基于Jana等人有关PBI在浓磷酸中热可逆溶胶凝胶的研究,提出利用PBI-H3PO4的溶胶凝胶化法制备PBI/H3PO4凝胶膜。再通过在低浓度磷酸溶液中的酸调节过程制备不同酸掺杂水平的PBI/H3PO4膜。与采用有机溶剂的溶液浇注法相比,这种方法简便易行,同时也避免了有机溶剂的使用。通过本方法制备的酸掺杂水平5.2的PBI/H3PO4膜,120℃时的电导率、断裂拉伸强度分别为2.4×10-2S/cm与5.1 MPa。
研究了PBI/H3PO4凝胶膜在低浓度磷酸溶液中的酸调节过程。发现与纯PBI膜的磷酸掺杂过程相比,PBI/H3PO4膜的磷酸去掺杂过程非常迅速。酸调节过程在降低膜磷酸掺杂水平、增加膜断裂拉伸强度的同时,也引起PBI膜的收缩。得到的PBI/H3PO4膜的酸掺杂水平主要受控因素为酸调节过程所用的磷酸浓度,而与酸调节过程温度关系不大。但温度越高,酸调节过程所需时间越短,得到的PBI/H3PO4膜也更致密。通过XRD研究发现磷酸掺杂会增加PBl分子骨架间距离,导致PBI膜的断裂拉伸强度降低。
Polybenzimidazole (PBI) membranes are used as membrane electrolyte materials for high temperature pronton exchange membrane fuel cells (HT-PEMFCs) working at 120-200℃due to its excellent thermal and chemical stabilities. The proton conductivity of the pure PBI membrane is as low as about 10-7 S/cm at room temperature, therefore PBI membranes need to be modified by doping with phosphoric acid for using as the proton exchange membrane electrolyte. PBI membranes are usually prepared by means of solution casting method. However, the PBI solubility in organic solvents, such as DMAc, decreases obviously with the increase of PBI molecular weight owing to its very rigid molecular structure. The restricted solubility of PBI in organic solvents results in a difficulty of preparation of PBI membranes especially when polymer has a high molecular weight. Therfore, direct casting acid doped PBI membrane was proposed by preparation of PBI solutions in mixed acids of triluoroacetic acid and phosphoric acid. N-substituted polybenzimidazoles by introducing ether linkage, side-chain alkyl and hexafluoropropyl in the polymer backbones have also been synthesized in order to improve the solubility. But these methods may increase the cost of preparing membranes or sacrifice the brand PBI properties to improve the processibility.
Jana et al. studied the thermoreversible gelation of PBI in phosphoric acid. This provides us a route to prepare the acid doped PBI membranes by conveniently dissolving PBI powders in phosphoric acid without organic solvents. Based on this sdudy, we prepared PBI membranes with various acid doping levels controlled by means of acid de-doping. The PBI-H3PO4 Sol-gel method shortens experiment period and doesn't use organic solwents at the same time. For a PBI membrane with an acid doping level of 5.2, the stress at break and proton conductivity at 120℃without humidification were 5.1 MPa and 2.4×10-2 S/cm, respectively.
The process for acid de-doping of the membranes was investigated. The process of the acid de-doping from the membrane was faster than of acid doping in the membrane. The de-doped acid molecules caused the shrinkage of the PBI membrane and thus the increase of the membrane strength due to the closeness of PBI chains according to the X-ray diffraction analysis. The acid doping level of PBI membranes only depends on the concentration of phosphoric acid used for acid de-doping. When acid de-doping process occurred in H3PO4 solvent at boiling point, it made membranes denser and cost less time than at room temperature. The increased separation of PBI backbones for PBI membranes by doped with phosphoric acids is confirmed by the analysis of XRD patterns.
本文基于Jana等人有关PBI在浓磷酸中热可逆溶胶凝胶的研究,提出利用PBI-H3PO4的溶胶凝胶化法制备PBI/H3PO4凝胶膜。再通过在低浓度磷酸溶液中的酸调节过程制备不同酸掺杂水平的PBI/H3PO4膜。与采用有机溶剂的溶液浇注法相比,这种方法简便易行,同时也避免了有机溶剂的使用。通过本方法制备的酸掺杂水平5.2的PBI/H3PO4膜,120℃时的电导率、断裂拉伸强度分别为2.4×10-2S/cm与5.1 MPa。
研究了PBI/H3PO4凝胶膜在低浓度磷酸溶液中的酸调节过程。发现与纯PBI膜的磷酸掺杂过程相比,PBI/H3PO4膜的磷酸去掺杂过程非常迅速。酸调节过程在降低膜磷酸掺杂水平、增加膜断裂拉伸强度的同时,也引起PBI膜的收缩。得到的PBI/H3PO4膜的酸掺杂水平主要受控因素为酸调节过程所用的磷酸浓度,而与酸调节过程温度关系不大。但温度越高,酸调节过程所需时间越短,得到的PBI/H3PO4膜也更致密。通过XRD研究发现磷酸掺杂会增加PBl分子骨架间距离,导致PBI膜的断裂拉伸强度降低。
Polybenzimidazole (PBI) membranes are used as membrane electrolyte materials for high temperature pronton exchange membrane fuel cells (HT-PEMFCs) working at 120-200℃due to its excellent thermal and chemical stabilities. The proton conductivity of the pure PBI membrane is as low as about 10-7 S/cm at room temperature, therefore PBI membranes need to be modified by doping with phosphoric acid for using as the proton exchange membrane electrolyte. PBI membranes are usually prepared by means of solution casting method. However, the PBI solubility in organic solvents, such as DMAc, decreases obviously with the increase of PBI molecular weight owing to its very rigid molecular structure. The restricted solubility of PBI in organic solvents results in a difficulty of preparation of PBI membranes especially when polymer has a high molecular weight. Therfore, direct casting acid doped PBI membrane was proposed by preparation of PBI solutions in mixed acids of triluoroacetic acid and phosphoric acid. N-substituted polybenzimidazoles by introducing ether linkage, side-chain alkyl and hexafluoropropyl in the polymer backbones have also been synthesized in order to improve the solubility. But these methods may increase the cost of preparing membranes or sacrifice the brand PBI properties to improve the processibility.
Jana et al. studied the thermoreversible gelation of PBI in phosphoric acid. This provides us a route to prepare the acid doped PBI membranes by conveniently dissolving PBI powders in phosphoric acid without organic solvents. Based on this sdudy, we prepared PBI membranes with various acid doping levels controlled by means of acid de-doping. The PBI-H3PO4 Sol-gel method shortens experiment period and doesn't use organic solwents at the same time. For a PBI membrane with an acid doping level of 5.2, the stress at break and proton conductivity at 120℃without humidification were 5.1 MPa and 2.4×10-2 S/cm, respectively.
The process for acid de-doping of the membranes was investigated. The process of the acid de-doping from the membrane was faster than of acid doping in the membrane. The de-doped acid molecules caused the shrinkage of the PBI membrane and thus the increase of the membrane strength due to the closeness of PBI chains according to the X-ray diffraction analysis. The acid doping level of PBI membranes only depends on the concentration of phosphoric acid used for acid de-doping. When acid de-doping process occurred in H3PO4 solvent at boiling point, it made membranes denser and cost less time than at room temperature. The increased separation of PBI backbones for PBI membranes by doped with phosphoric acids is confirmed by the analysis of XRD patterns.
引文
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