基于乙烯基加成型聚降冰片烯衍生物质子交换膜的制备及性能
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摘要
直接甲醇燃料电池(DMFC)具有使用安全、能量密度高、环境友好等特点,已成为当今能源领域的研究热点。其中质子交换膜是直接甲醇燃料电池的核心组件之一,目前商用的Nafion(?)膜,因其甲醇透过率高、高温低湿条件下质子传导率急剧降低、尺寸稳定性差、环境污染严重及制备成本昂贵等缺点,制约了其进一步推广。开发高性价比的新型质子交换膜已成为直接甲醇燃料电池研究中热点。加成型聚降冰片烯(PNB)材料有良好的成膜性、热稳定性、高的玻璃化转变温度、优异的阻醇性能及良好的化学稳定性等优点,并且其主链中保留了双环结构因而具有高尺寸稳定性、优异的抗离子蚀刻能力和电绝缘性能是适合开发作为直接甲醇燃料电池用质子交换膜的良好材料。
本文以双-(β-酮萘亚胺)镍(Ⅱ)与B(C6F5)3的二元催化体系催化5-降冰片烯-2-亚甲基丁基醚(2-butoxymethylenyl-5-norbornene, NBF1, NB=norbornene, F1=-CH2-O-CH2CH2CH2CH3)与5-降冰片烯-2-亚甲基醋酸酯(2-methylenyl acetate-5-norbornene, NBF2, F2=-CH2-O-COCH3)加成聚合,得到共聚物聚(5-降冰片烯-2-亚甲基丁基醚-共-5-降冰片烯-2-亚甲基醋酸酯)(PNBF1/NBF2-91,91表示NBF1与NBF2的摩尔投料比为9：1),然后脱酯得到含羟基的聚(5-降冰片烯-2-亚甲基丁基醚-共-5-降冰片烯-2-亚甲醇)(PNBF1/NBF3-91, F3=-CH2-OH)。PNBF1/NBF3-91溶于THF,然后加入不同比例的咪唑-4,5-二羧酸(IDA)和H3P04,使IDA的羧酸基团与PNBF1/NBF3-91的羟基发生酯化交联,H3P04与IDA形成咪唑-磷酸络合物,制备系列PNBF1/NBF3-91/IDA/H3PO4交联膜(PNBIH)。对其断面形貌、吸水率、质子传导率、甲醇透过率、热稳定性和机械他性能等进行了表征,结果表明PNBIH膜的质子传导率随着温度和IDA/H3PO4含量的增加而增大,PNBIH膜有优异的阻醇性能其甲醇透过率为0.25×10-6至0.42×10-6cm2·s-1,比商业化的Nafion115(N115)膜低一个数量级。
在上述催化体系下,改变NBF1和NBF2的投料比合成系列聚合物PNBF1/NBF3-xx (xx表示NBF1与NBF2的摩尔投料比从9：1到5：5),利用活性基团-OH与1,4-丁磺酸内酯反应,成功合成了含有磺酸基团的磺化聚降冰片烯(SPNBF1/NBF3-xx),通过1HNMR、FT-IR证实了共聚物的结构。SPNBF1/NBF3-xx的溶解性能较差,仅SPNBF1/NBF3-91可溶于THF制备了质子交换膜。为了增强该膜的质子传导率,我们往SPNBF1/NBF3-91聚合物溶液中加入一定量的PNBF1/NBF3-91、IDA和H3P04制备了复合质子交换膜。复合膜和SPNBF1/NBF3-91膜都有很好的尺寸稳定性和阻醇性能,SPNBF1/NBF3-91与复合膜的甲醇透过率分别为0.87×10-7cm2·s-1和1.83×10-7 cm2·s-1,远低于N115(11.73×10-7 cm2·s-1),但是SPNBF1/NBF3-91质子传导率过低,不能得到单电池的相关数据。复合膜组装的MEA在70℃和2mol·L-1的甲醇的工作环境下,开路电压为0.483 V略低于N115的0.559 V,但其输出功率仅有1.35mW·cm-2要低于N115(16mW-cm-2)。
Direct methanol fuel cells (DMFCs) have been one of priority development of the energy technologies due to their high power density, environment friendly and security. The proton exchange membrane (PEM) is one of the key components determining the performance of the fuel cells. Nafion(?) is the current state-of-the-art PEM material, while several drawbacks of Nafion(?), such as high cost, high methanol permeability, low humidity and a major reduction in conductivity at high temperatures, has limited its industrial applications. These limitations have stimulated worldwide research activities for developing new materials with high performance as proton exchange membrane.
Vinyl addition type polynorbornenes exhibit good membrane formation, high thermal stability, excellent methanol resistant, high glass transition temperature and good chemical stability. Because all this materials that have dual-ring structure, usually have high dimensional stability and excellent dielectric properties etc., the vinyl addition type polynorbornene is suitable for development as a direct methanol fuel cell proton exchange membrane material.
The poly (2-butoxymethylenyl-5-norbornene-co-2-methylenyl acetate-5-norbornene) (PNBF1/NBF2-91,91 indicate the mole feed rate of NBF,:NBF2 is 9:1) was successfully synthesized via the vinyl addition copolymerization of 2-butoxymethylenyl-5-norbornene (NBF1, NB=norbornene, F1=-CH2-O-CH2CH2CH2CH3) and 2-methylenyl acetate-5-norbornene (NBF2, F2=-CH2-O-COCH3) by using bis-((β-ketonaphthylamino)nickel(Ⅱ)/B(C6F5)3 catalytic system. The poly (2-butoxymethylenyl-5-norbornene-co-2-methylol-5-norbornene) (PNBF1/ NBF3-91, F3=-CH2-OH) was obtained by the de-esterification of PNBFi/NBF2-91. Then PNBF1/NBF3-91 was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the-OH groups and the-COOH groups of IDA. Upon doping with phosphoric acid (H3PO4) to form imidazole-H3PO4 complexes to obtain the PNBF1/NBF3-91/IDA/H3PO4 (PNBIH) cross-linked membranes and the corresponding morphology, water uptake, proton conductivity, methanol permeability, thermal stability, as well as tensile properties were investigated. The results indicate that the crosslinked membranes showed higher proton conductivity at higher temperatures and lower methanol permeability after incorporation of more content of IDA and H3PO4. The PNBIH membranes showed lower methanol permeability from 0.25×10-6 to 0.4×10-6 cm2·s-1, which is order of magnitude lower than that of N115.
The sulfonated functional polynorbornenes (SPNBF1/NBF3-xx) are successfully prepared via the sulfobutylation of the PNBF1/NBF3-xx (xx is the mole feed ratio of NBF1 and NBF2 is from 9:1 to 5:5) with 1,4-butane sultone, and the chemical structures of the polymers are confirmed by the 1H NMR and the FT-IR. Except for SPNBF1/NBF3-91, the rest SPNBF1/NBF3-xx can not be dissolved in common organic solvents. So the PEM membrane is only from SPNBF1/NBF3-91, With the purpose of improving the proton conductivity of SPNBF1/NBF3-91 membrane, a composite membrane with a proper content of PNBF1/NBF3-91 copolymer, IDA and H3PO4, has been prepared. The SPNBF1/NBF3-91 and its blend membranes have excellent methanol resistant and dimensional stability, and the methanol permeability of the SPNBF1/NBF3-91 and its blend membranes are 0.87×10-7 cm2 and 1.83×10-7 cm2·s-1, respectively. But SPNBF1/NBF3-91 membrane with so poor proton conductivity that can not obtained its DMFC performance. Compare with the N115 (0.559 V,16 mW·cm-2), open circuit voltages (0.483 V) of the blend membrane at 2 mol·L-1 methanol (70℃) exhibited only slightly lower, while its power density decreases sharply to 1.35 mW·cm-2.
本文以双-(β-酮萘亚胺)镍(Ⅱ)与B(C6F5)3的二元催化体系催化5-降冰片烯-2-亚甲基丁基醚(2-butoxymethylenyl-5-norbornene, NBF1, NB=norbornene, F1=-CH2-O-CH2CH2CH2CH3)与5-降冰片烯-2-亚甲基醋酸酯(2-methylenyl acetate-5-norbornene, NBF2, F2=-CH2-O-COCH3)加成聚合,得到共聚物聚(5-降冰片烯-2-亚甲基丁基醚-共-5-降冰片烯-2-亚甲基醋酸酯)(PNBF1/NBF2-91,91表示NBF1与NBF2的摩尔投料比为9：1),然后脱酯得到含羟基的聚(5-降冰片烯-2-亚甲基丁基醚-共-5-降冰片烯-2-亚甲醇)(PNBF1/NBF3-91, F3=-CH2-OH)。PNBF1/NBF3-91溶于THF,然后加入不同比例的咪唑-4,5-二羧酸(IDA)和H3P04,使IDA的羧酸基团与PNBF1/NBF3-91的羟基发生酯化交联,H3P04与IDA形成咪唑-磷酸络合物,制备系列PNBF1/NBF3-91/IDA/H3PO4交联膜(PNBIH)。对其断面形貌、吸水率、质子传导率、甲醇透过率、热稳定性和机械他性能等进行了表征,结果表明PNBIH膜的质子传导率随着温度和IDA/H3PO4含量的增加而增大,PNBIH膜有优异的阻醇性能其甲醇透过率为0.25×10-6至0.42×10-6cm2·s-1,比商业化的Nafion115(N115)膜低一个数量级。
在上述催化体系下,改变NBF1和NBF2的投料比合成系列聚合物PNBF1/NBF3-xx (xx表示NBF1与NBF2的摩尔投料比从9：1到5：5),利用活性基团-OH与1,4-丁磺酸内酯反应,成功合成了含有磺酸基团的磺化聚降冰片烯(SPNBF1/NBF3-xx),通过1HNMR、FT-IR证实了共聚物的结构。SPNBF1/NBF3-xx的溶解性能较差,仅SPNBF1/NBF3-91可溶于THF制备了质子交换膜。为了增强该膜的质子传导率,我们往SPNBF1/NBF3-91聚合物溶液中加入一定量的PNBF1/NBF3-91、IDA和H3P04制备了复合质子交换膜。复合膜和SPNBF1/NBF3-91膜都有很好的尺寸稳定性和阻醇性能,SPNBF1/NBF3-91与复合膜的甲醇透过率分别为0.87×10-7cm2·s-1和1.83×10-7 cm2·s-1,远低于N115(11.73×10-7 cm2·s-1),但是SPNBF1/NBF3-91质子传导率过低,不能得到单电池的相关数据。复合膜组装的MEA在70℃和2mol·L-1的甲醇的工作环境下,开路电压为0.483 V略低于N115的0.559 V,但其输出功率仅有1.35mW·cm-2要低于N115(16mW-cm-2)。
Direct methanol fuel cells (DMFCs) have been one of priority development of the energy technologies due to their high power density, environment friendly and security. The proton exchange membrane (PEM) is one of the key components determining the performance of the fuel cells. Nafion(?) is the current state-of-the-art PEM material, while several drawbacks of Nafion(?), such as high cost, high methanol permeability, low humidity and a major reduction in conductivity at high temperatures, has limited its industrial applications. These limitations have stimulated worldwide research activities for developing new materials with high performance as proton exchange membrane.
Vinyl addition type polynorbornenes exhibit good membrane formation, high thermal stability, excellent methanol resistant, high glass transition temperature and good chemical stability. Because all this materials that have dual-ring structure, usually have high dimensional stability and excellent dielectric properties etc., the vinyl addition type polynorbornene is suitable for development as a direct methanol fuel cell proton exchange membrane material.
The poly (2-butoxymethylenyl-5-norbornene-co-2-methylenyl acetate-5-norbornene) (PNBF1/NBF2-91,91 indicate the mole feed rate of NBF,:NBF2 is 9:1) was successfully synthesized via the vinyl addition copolymerization of 2-butoxymethylenyl-5-norbornene (NBF1, NB=norbornene, F1=-CH2-O-CH2CH2CH2CH3) and 2-methylenyl acetate-5-norbornene (NBF2, F2=-CH2-O-COCH3) by using bis-((β-ketonaphthylamino)nickel(Ⅱ)/B(C6F5)3 catalytic system. The poly (2-butoxymethylenyl-5-norbornene-co-2-methylol-5-norbornene) (PNBF1/ NBF3-91, F3=-CH2-OH) was obtained by the de-esterification of PNBFi/NBF2-91. Then PNBF1/NBF3-91 was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the-OH groups and the-COOH groups of IDA. Upon doping with phosphoric acid (H3PO4) to form imidazole-H3PO4 complexes to obtain the PNBF1/NBF3-91/IDA/H3PO4 (PNBIH) cross-linked membranes and the corresponding morphology, water uptake, proton conductivity, methanol permeability, thermal stability, as well as tensile properties were investigated. The results indicate that the crosslinked membranes showed higher proton conductivity at higher temperatures and lower methanol permeability after incorporation of more content of IDA and H3PO4. The PNBIH membranes showed lower methanol permeability from 0.25×10-6 to 0.4×10-6 cm2·s-1, which is order of magnitude lower than that of N115.
The sulfonated functional polynorbornenes (SPNBF1/NBF3-xx) are successfully prepared via the sulfobutylation of the PNBF1/NBF3-xx (xx is the mole feed ratio of NBF1 and NBF2 is from 9:1 to 5:5) with 1,4-butane sultone, and the chemical structures of the polymers are confirmed by the 1H NMR and the FT-IR. Except for SPNBF1/NBF3-91, the rest SPNBF1/NBF3-xx can not be dissolved in common organic solvents. So the PEM membrane is only from SPNBF1/NBF3-91, With the purpose of improving the proton conductivity of SPNBF1/NBF3-91 membrane, a composite membrane with a proper content of PNBF1/NBF3-91 copolymer, IDA and H3PO4, has been prepared. The SPNBF1/NBF3-91 and its blend membranes have excellent methanol resistant and dimensional stability, and the methanol permeability of the SPNBF1/NBF3-91 and its blend membranes are 0.87×10-7 cm2 and 1.83×10-7 cm2·s-1, respectively. But SPNBF1/NBF3-91 membrane with so poor proton conductivity that can not obtained its DMFC performance. Compare with the N115 (0.559 V,16 mW·cm-2), open circuit voltages (0.483 V) of the blend membrane at 2 mol·L-1 methanol (70℃) exhibited only slightly lower, while its power density decreases sharply to 1.35 mW·cm-2.
引文
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