CN102044648B - 聚芳基醚苯并咪唑离子交换膜及其制备和全钒液流电池 - Google Patents

聚芳基醚苯并咪唑离子交换膜及其制备和全钒液流电池 Download PDF

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CN102044648B
CN102044648B CN200910187902XA CN200910187902A CN102044648B CN 102044648 B CN102044648 B CN 102044648B CN 200910187902X A CN200910187902X A CN 200910187902XA CN 200910187902 A CN200910187902 A CN 200910187902A CN 102044648 B CN102044648 B CN 102044648B
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张华民
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毕成
肖少华
麦振声
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Abstract

本发明涉及适用于全钒氧化还原液流电池的一种聚芳基醚苯并咪唑离子交换膜及其制备方法。本发明还涉及包含本发明聚合物离子交换膜的全钒氧化还原液流电池。本发明聚芳基醚苯并咪唑离子交换膜的制备条件温和，制备工艺简单，有利于实现批量生产。通过调节醚键和咪唑环的比例，制备的聚芳基醚苯并咪唑离子交换膜具有优良力学强度的同时具有良好的韧性，其在全钒氧化还原液流电池中具有优良的质子传导性能和优异的阻隔钒离子渗透性能。

Description

聚芳基醚苯并咪唑离子交换膜及其制备和全钒液流电池
技术领域
本发明涉及一种聚芳基醚苯并咪唑离子交换膜及其制备方法，特别涉及该聚芳基醚苯并咪唑离子交换膜在全钒氧化还原液流电池中的应用。
背景技术
全钒氧化还原液流电池是以不同价态钒离子硫酸溶液作为电解液、以离子交换膜为隔膜的新型储能电池，具有容量和功率可调、大电流无损深度放电、使用寿命长、易操作和维护等优点，通过对现有电网系统“削峰填谷”，将不稳定的电能输入变为连续、安全可靠的电能输出，改善电网安全性和可靠性，是风力、太阳能发电领域理想的储能系统，具有广阔的应用空间。
全钒氧化还原液流的隔膜是核心部件。液流电池的性能和成本在很大程度上取决于所用的膜材料。全钒氧化还原液流电池用隔膜要求具有优异的化学稳定性，良好的质子传导性能和良好的阻钒离子渗透性能。目前使用的隔膜主要是杜邦公司生产的全氟磺酸离子交换膜(
Figure G200910187902XD00011
膜)，虽然其具有优异的化学稳定性和质子传导性能，但是高昂的价格和较高的钒离子透过率限制了其广泛应用。因此，开发低成本、高性能的全钒氧化还原液流电池用隔膜是液流电池领域十分关注的课题。
聚苯并咪唑是一种碱性聚合物(pKa＝5.5)，能够与强酸杂化而形成一种酸掺杂体系而具备传导质子的能力，文献(Xavier Glipa，J.Mater.Chem.，1999，9，3045-3049)报道磷酸和硫酸掺杂的聚苯并咪唑膜室温下的质子电导率数量级在10-3S cm-1，进一步提高温度膜的质子传导能力进一步提高。因而，磷酸掺杂的聚苯并咪唑膜被广泛用于高温质子交换膜燃料电池领域。全钒氧化还原液流电池采用不同价态钒离子的硫酸溶液作为电解液，因而，硫酸掺杂的聚苯并咪唑膜能够用作全钒氧化还原液流电池隔膜起传导质子的作用。目前，市场上唯一商业化的聚苯并咪唑树脂为聚[2，2’-(间-亚苯基)-5，5’-二苯并咪唑]，该树脂存在难熔融、难溶解、难加工的缺陷。其成膜过程先将树脂在高温250℃加压条件下溶解在有机溶剂如N，N-二甲基乙酰胺(沸点165℃)中，再浇铸成膜(Journal of Membrane Science，2006，280，351-362)。成膜过程对实验装置要求较高，操作条件较为苛刻。而且，全芳香结构的聚[2，2’-(间-亚苯基)-5，5’-二苯并咪唑]制备的膜刚性太强，缺乏韧性。全钒氧化还原液流电池的工作环境要求膜具有良好力学强度的同时还需要具有良好的韧性，以应对电池组装力和长期的流体冲刷产生的作用力。因此，从液流电池实际应用的角度来看，应当有针对性的开发具有良好溶解和加工性能的聚苯并咪唑树脂，能够在较温和的条件下制备酸掺杂的聚并咪唑离子交换膜，得到成本低廉、在全钒氧化还原液流电池中具有良好性能的离子交换膜，得到成本低廉、具有良好韧性、在全钒氧化还原液流电池中具有良好性能的离子交换膜。
发明内容
本发明的目的在于提供一种聚芳基醚苯并咪唑离子交换膜及其制备方法，以及其在全钒液流电池中的应用。
本发明的聚芳基醚苯并咪唑膜的结构通式如下：
Figure G200910187902XD00021
其中：0＜y＜1，n＝20～2000
R1代表：
Figure G200910187902XD00022
R2代表：
Figure G200910187902XD00023
中的一种；
R3代表：
中的一种；
本发明所述的聚芳基醚苯并咪唑离子交换膜的制备方法，包括如下步骤：
(1)将P2O5溶解在CH3SO3H中形成澄清溶液，其中P2O5与CH3SO3H的重量比为0.8∶10～2∶10。
(2)将3，4-二氨基苯甲酸，含醚键二元羧酸和芳香四元胺以一定的摩尔比加入到步骤1配制的溶液中。其中含醚键二元羧酸和芳香四元胺加入的摩尔数之比为1∶1，含醚键二元羧酸和芳香四元胺的摩尔数之和与3，4-二氨基苯甲酸的摩尔数之比为9∶1～5∶5，三种单体重量占整个体系重量的8～20％。在惰性气体保护条件下，于120～160℃反应10～300min后，得到聚芳基醚苯并咪唑溶液。
(3)将得到的聚芳基醚苯并咪唑溶液直接浇铸于玻璃板或不锈钢板上，于60～100℃下干燥5h以上，然后80～150℃真空干燥1h以上成膜，将膜浸泡在去离子水或乙醇中2天以上除去膜中残留的CH3SO3H；将制备的膜浸入硫酸或者磷酸1h以上，得到聚芳基醚苯并咪唑离子交换膜，膜的厚度在10～200μm之间。
所述的含醚键二元羧酸为4，4’-羟基二苯甲酸，4，4’-[(1，4-亚苯基)双氧]二苯甲酸，4，4’-[2-苯基-(1，4-亚苯基)双氧]二苯甲酸中的一种。
所述的芳香四元胺为：3，3，4，4’-四氨基联苯，2，3，6，7-萘四胺，1，2，4，5-苯四胺，3，3，4，4’-四氨基二苯醚，3，3，4，4’-四氨基二苯硫醚，3，3，4，4’-四氨基二苯砜，3，3，4，4’-四氨基二苯酮，3，3，4，4’-四氨基二苯基甲烷2，2-二(3，4-二氨基苯基)丙烷或2，2-二(3，4-二氨基苯基)六氟丙烷。
所述的硫酸和磷酸的浓度在1～16mol L-1之间。
本发明还提供包括本方法制备的聚芳基醚苯并咪唑离子交换膜的全钒氧化还原液流电池。
本发明的有益结果是：(1)本发明通过选择活性较高的含醚键二元羧酸与3，4-二氨基苯甲酸和芳香四元胺反应，合成聚芳醚基苯并咪唑的条件温和，通过将反应溶液直接浇铸制备聚合物膜的工艺操作步骤简单，有利于实现批量生产。(2)单体3，4-二氨基苯甲酸由于同时含有氨基和羧酸基团，在本实验条件下，能够在发生自聚的同时和含醚键二元羧酸、芳香四元胺发生共聚。便于调节聚合物体系中醚键和咪唑环的比例。(3)通过调节三种反应单体的比例来调节聚芳醚基苯并咪唑中醚键的含量，制备的聚芳基醚苯并咪唑离子交换膜既具有优异的力学性能又具有良好的韧性，同时具有良好的抗氧化性能。(4)聚芳基醚苯并咪唑离子交换膜应用于全钒氧化还原液流电池具有优良的质子传导性能和优异的阻隔钒离子渗透性能。
附图说明
图1为实施例1干态聚芳基醚苯并咪唑膜的拉伸曲线。
图2为实施例1聚芳基醚苯并咪唑离子交换膜的拉伸曲线。
图3为实施例6聚芳基醚苯并咪唑离子交换膜的全钒氧化还原电池在50mA cm-2时的充放电曲线。
具体实施方式
下面的实施例是对本发明的进一步说明，而不是限制本发明的范围。
实施例1
将P2O5和CH3SO3H以重量比为1∶10的比例在加热搅拌条件下混合形成均匀透明的溶液，取200ml加入干燥的三颈烧瓶中，然后将4.56g 3，4-二氨基苯甲酸，18.1g 4，4’-羟基二苯甲酸和15.0g 3，3，4，4’-四胺基联苯加入三颈烧瓶充分溶解，缓慢加热至140℃，然后反应60min，得到粘稠的聚合物溶液，将聚合物溶液倾倒在平铺的玻璃板上，用铸模刀推平，于60℃干燥20h后真空110℃干燥10h。将膜从玻璃板上取下，用去离子水和乙醇洗涤除去残留的CH3SO3H，取出烘干得到干态的聚合物膜。溶解在二甲亚砜中配成0.5gL-1的溶液，用旋转粘度仪测得其固有粘度为2.4dL g-1，干态聚合物膜的拉伸曲线见图1，膜的拉伸强度为134MPa，断裂伸长率为12.3％，表明聚合物具有较高的分子量，制备的膜具有很好的强度和一定的韧性。聚合物膜1H NMR：(500MHz，DMSO-d6)，δ13.10(s，3H)，δ8.53(s，1H)，δ8.20-8.30(m，6H)，δ7.65-7.80(m，6H)，δ7.30(d，4H)。FTIR分析：3450-3250cm-2，γ(N-H)；1630cm-2，γ(C＝N)；1243cm-2和1171cm-2，γ(Ar-O-Ar)；1443cm-2，γ(2，6-二取代咪唑环的面内环振动特征吸收峰)。
将干态聚合物膜室温浸泡在4M硫酸中处理3h，得到厚度为35μ的聚芳基醚苯并咪唑离子交换膜。膜的拉伸曲线见图2，膜的拉伸强度为67MPa，断裂伸长率为23％，表明制备的离子交换膜维持了良好的强度和韧性。
实施例2
同实施例1，用6M磷酸取代硫酸将膜室温浸泡处理3天，取出并烘干得到厚度为45μ的聚芳基醚苯并咪唑离子交换膜。膜的拉伸强度为90MPa，断裂伸长率为28％。
实施例3
同实施例1，用12M磷酸取代硫酸将膜室温浸泡处理3天，取出并烘干得到厚度为80μ的聚芳基醚苯并咪唑离子交换膜。膜的拉伸强度为35MPa，断裂伸长率为95％。
实施例4
将P2O5和CH3SO3H以重量比为0.8∶10的比例在加热搅拌条件下混合形成均匀透明的溶液，取100ml加入干燥的三颈烧瓶中，然后将1.52g 3，4-二氨基苯甲酸，10.32g 4，4’-羟基二苯甲酸和8.57g 3，3，4，4’-四胺基联苯加入三颈烧瓶充分溶解，缓慢加热至160℃，然后反应50min，得到粘稠的聚合物溶液，将聚合物溶液倾倒在平铺的玻璃板上，用铸模刀推平，于60℃干燥20h后真空110℃干燥10h。将膜从玻璃板上取下，用去离子水和乙醇洗涤除去残留的CH3SO3H，取出烘干。聚合物膜1H NMR：(500MHz，DMSO-d6)，δ13.10(s，3H)，δ8.53(s，1H)，δ8.20-8.30(m，6H)，δ7.65-7.80(m，6H)，δ7.30(d，4H)。FTIR分析：3450-3250cm-2，γ(N-H)；1630cm-2，γ(C＝N)；1243cm-2和1171cm-2，γ(Ar-O-Ar)；1443cm-2，γ(2，6-二取代咪唑环的面内环振动特征吸收峰)。
将干态聚合物膜室温浸泡在10M磷酸中处理72h，烘干得到厚度为70μ的聚芳基醚苯并咪唑离子交换膜。膜的拉伸强度为45MPa，断裂伸长率为83％。
实施例5
同实施例4，用3M硫酸取代磷酸将膜室温浸泡处理3天，取出得到厚度为40μ的聚芳基醚苯并咪唑离子交换膜。膜的拉伸强度为60MPa，断裂伸长率为32％。
实施例6
将实施例1中的聚芳基醚苯并咪唑离子交换膜组装全钒氧化还原液流电池，活性碳毡为催化层，石墨板为双极板，膜有效面积为6cm-2，电流密度为50mA cm-2，电解液中钒离子浓度为1.50mol L-1，H2SO4浓度为3mol L-1。组装的液流电池电流效率为97.2％，电压效率为85.1％，能量效率为82.6％。电池充放电曲线见图3，图中充电时间和放电时间基本相当，放电相当平缓，表明膜的钒渗透率相当低。
实施例7
将实施例5中的聚芳基醚苯并咪唑离子交换膜组装全钒氧化还原液流电池，其他条件同实施例6。组装的液流电池电流效率为97％，电压效率为84.5％，能量效率为82.0％。
比较例
与实施例6和7相比，将膜换成杜邦公司生产的Nafion 115膜，其他条件不变。电池电流效率为90.2％，电压效率为91.9％，能量效率为82.9％。与商业化的Nafion相比，制备的聚芳基醚苯并咪唑离子交换膜在能量效率相当的前提下，电流效率显著提高(提高7个百分点)。

Claims (6)

1.一种聚芳基醚苯并咪唑离子交换膜，其特征在于：结构通式如下，
Figure FDA00002087232900011
其中：0<y<1,n＝20～2000
R1代表：
Figure FDA00002087232900012
R2代表：
Figure FDA00002087232900013
中的一种；
R3代表：
Figure FDA00002087232900014
中的一种。
2.一种权利要求1所述聚芳基醚苯并咪唑离子交换膜的制备方法，其特征在于：包括如下步骤，
(1)将P2O5溶解在CH3SO3H中形成澄清溶液，其中P2O5与CH3SO3H的重量比为0.8:10～2:10；
(2)将3,4-二氨基苯甲酸，含醚键二元羧酸和芳香四元胺以一定的摩尔比加入到步骤1配制的溶液中；其中含醚键二元羧酸和芳香四元胺加入的摩尔数之比为1:1，含醚键二元羧酸和芳香四元胺的摩尔数之和与3,4-二氨基苯甲酸的摩尔数之比为9:1～5:5，三种单体总重量占整个体系总重量的8～20%；
在惰性气体保护条件下，于120～160℃反应10～300min后，得到聚芳基醚苯并咪唑溶液；
(3)将得到的聚芳基醚苯并咪唑溶液直接浇铸于玻璃板或不锈钢板上，于60～100℃下干燥5h以上，然后80～150℃真空干燥1h以上成膜，将膜浸泡在去离子水或乙醇中2天以上除去膜中残留的CH3SO3H；将制备的膜浸入硫酸或者磷酸1h以上，得到聚芳基醚苯并咪唑离子交换膜，膜的厚度在10～200μm之间。
3.根据权利要求2所述的制备方法，其特征在于：含醚键二元羧酸为4,4’-羟基二苯甲酸，3,3’-(间-亚苯基双氧)二苯甲酸，4,4’-(间-亚苯基双氧)二苯甲酸中的一种。
4.根据权利要求2所述的制备方法，其特征在于：
芳香四元胺为：3,3’,4,4’-四氨基联苯，2,3,6,7-萘四胺，1,2,4,5-苯四胺，3,3’,4,4’-四氨基二苯醚，3,3’,4,4’-四氨基二苯硫醚，3,3’,4,4’-四氨基二苯砜，3,3’,4,4’-四氨基二苯酮，3,3’,4,4’-四氨基二苯基甲烷、2,2-二(3,4-二氨基苯基)丙烷或2,2-二(3,4-二氨基苯基)六氟丙烷中的一种。
5.根据权利要求2所述的制备方法，其特征在于：硫酸或磷酸的浓度在1～16mol·L-1之间。
6.一种全钒氧化还原液流电池，其特征是：其所应用的离子交换膜为权利要求1的聚芳基醚苯并咪唑离子交换膜。
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