CN117691146A - 液流电池双极板制备工艺 - Google Patents
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Abstract
本发明涉及储能充放电电池零件制备技术领域,具体为液流电池双极板制备工艺,目的是使双极板导电性高、强度高、成本低和制造简便,具有如下过程,(1)、将可膨胀石墨与导电添加剂的混合物辊压成表面无气泡的石墨预制板;(2)、将碳纤维布碳化或石墨化处理成碳毡;(3)、自下而上依次层叠热塑膜、石墨预制板、热塑膜、碳毡、热塑膜、石墨预制板和热塑膜,在加温加压状态下对层叠板进行压制;(4)冷却定型成双极板板材,经分切成为液流电池双极板;过程(3)中对层叠板的加温加压使热塑膜熔融后成为渗入石墨预制板和渗入石墨预制板与碳毡的粘接剂,所以,层叠板的加温温度大于层叠板中热塑膜的熔点温度。
Description
技术领域
本发明涉及储能充放电电池零件制备技术领域,具体为液流电池双极板制备工艺。
背景技术
双极板是组装成电池堆的关键部件之一,用于实现多个单电池的串联与分隔、电池中产生的电流的传导,并且为液流电池中的反应电极提供支撑,正侧与单电池阳极接触,反侧与另一个单电池的阴极接触,电堆是将单个电池串联起来而组成的。
鉴于双极板的重要特性,因此对双极板的要求很高,要求是:
1.双极板材料电阻率低、稳定性高、致密性强以及抗腐蚀性强;
2.较低的热膨胀率和离子透过率,确保长期有效的使用寿命;
3.电堆中单电池数量大,电池中的零件需要成本低、制造简便。
目前,应用于大规模液流电池领域的双极板结构形式主要为两类,即碳素双极板和柔性石墨双极板,碳素类双极板为高比例树脂与导电材料的混合成型,优点是机械强度高、稳定性高,缺点是由于其树脂含量高、导致材料产品的导电性差;而柔性石墨双极板采用浸渍树脂的膨胀石墨预制板成型,其优点是导电性高,但机械强度低,同时,在规模化生产时,树脂浸渍难度大且耗时长,限制了双极板的规模化生产尺寸及效率。
发明内容
本发明要解决的技术问题是:提供一种液流电池双极板制备工艺,使双极板导电性高、强度高、成本低和制造简便。
本发明解决其技术问题所采用的技术方案是:一种液流电池双极板制备工艺,具有如下过程,
(1)、将可膨胀石墨与导电添加剂的混合物辊压成表面无气泡的石墨预制板;
(2)、将碳纤维布碳化或石墨化处理成碳毡;
(3)、自下而上依次层叠热塑膜、石墨预制板、热塑膜、碳毡、热塑膜、石墨预制板和热塑膜,在加温加压状态下对层叠板进行压制;
(4)冷却定型成双极板板材,经分切成为液流电池双极板;
过程(3)中对层叠板的加温加压使热塑膜熔融后成为渗入石墨预制板和渗入石墨预制板与碳毡的粘接剂,所以,层叠板的加温温度大于层叠板中热塑膜的熔点温度,若层叠板中包含不同种热塑膜时,则层叠板的加温温度大于所有热塑膜的熔点温度。
具体的,过程(1)中的可膨胀石墨与导电添加剂的重量百分比分别为99.9%~80%和0.1%~20%。
具体的,过程(1)中的导电添加剂中包括碳纳米管、石墨烯、导电炭黑、活性炭和导电纤维中一种或两种或两种以上组合物。
具体的,过程(2)中碳纤维布的克重为5~200g/cm2、厚度为20~500μm。
具体的,过程(3)中热塑膜为聚丙烯膜、聚乙烯膜、热塑型酚醛膜、聚苯硫醚膜或聚偏氟乙烯膜。
具体的,过程(3)中热塑膜厚度为10~400μm。
具体的,过程(3)中压机对层叠板的压力为1~50mpa, 层叠板的加热温度为80~350℃,时间为3~120min。
本发明的有益效果是:
一、采用可膨胀石墨与导电添加剂混合作为双极板的主体材料,保证了其导电性,同时导电添加剂的加入增加了导电网络的搭建;
二、采用石墨化碳纤维布作为中间夹层,进一步增强了柔性石墨双极板的机械强度;
三、将热塑膜加温加压为双极板内的粘结树脂,极大程度的简化了生产工艺和操作难度,避免了树脂浸渍带来的大面积双极板制备的加工难度;
四、采用多层树脂铺叠的方式,保证了双极板内部材质的均一性。
具体实施方式
本发明用下列实施例来进一步说明技术特征,但本发明的保护范围并非限于下列实施例。
实施例一:
一种液流电池双极板制备工艺,具有如下过程,
(1)、将可膨胀石墨与导电添加剂碳纳米管的混合物辊压成表面无气泡的石墨预制板,可膨胀石墨与碳纳米管的重量百分比分别为99.9%和0.1%,使用钢辊预压机,制成的石墨预制板厚度2mm;
(2)、将碳纤维布碳化处理成碳毡,碳纤维布的克重为5g/cm2、厚度为20μm;
(3)、自下而上依次层叠聚丙烯膜、石墨预制板、聚丙烯膜、碳毡、聚丙烯膜、石墨预制板和聚丙烯膜,聚丙烯膜厚度为10μm,加温加压状态下对层叠板进行压制,压机对层叠板的压力为1mpa, 层叠板的加热温度为高于聚丙烯熔点的180℃,时间为3min,层叠板压制后的厚度为1.5mm;
(4)冷却定型成双极板板材,经分切成为液流电池双极板;
过程(3)中对层叠板的加温加压使聚丙烯膜熔融后成为渗入相邻的石墨预制板和渗入相邻石墨预制板与碳毡的粘接剂。
实施例二:
一种液流电池双极板制备工艺,具有如下过程,
(1)、将可膨胀石墨与导电添加剂的混合物辊压成表面无气泡的石墨预制板,导电添加剂为石墨烯、活性炭和导电纤维的组合物,添加剂组合物中石墨烯、活性炭和导电纤维的重量比为4:3:3,可膨胀石墨与组合添加剂的重量百分比分别为80%和20%,使用钢辊预压机,制成的石墨预制板厚度10mm;
(2)、将碳纤维布石墨化处理成碳毡,碳纤维布的克重为200g/cm2、厚度为500μm;
(3)、自下而上依次层叠聚苯硫醚膜、石墨预制板、聚苯硫醚膜、碳毡、聚苯硫醚膜、石墨预制板和聚苯硫醚膜,聚苯硫醚膜厚度为400μm,加温加压状态下对层叠板进行压制,压机对层叠板的压力为50mpa, 层叠板的加热温度为高于聚苯硫醚熔点的350℃,时间为120min,层叠板压制后的厚度为2.5mm;
(4)冷却定型成双极板板材,经分切成为液流电池双极板;
过程(3)中对层叠板的加温加压使聚苯硫醚熔融后成为渗入石墨预制板和渗入石墨预制板与碳毡的粘接剂。
上述示例中每种方式都使用了同种热塑膜,这是为了便于确定加热温度,事实上根据粘接需要,也可以使用不同材质的热塑膜,厚度上也可以是不同的,毕竟,外层的热塑膜只渗入石墨预制板,而内层的热塑膜需同时渗入相邻的石墨预制板和碳毡,需要注意的是,选择热塑膜的材质和厚度时也要考虑避免板材最终出现内部应力,避免开裂和变形。
本发明制成的双极板与同样厚度现有碳素双极板性能上的测试情况见表1。
表1:本发明制成的双极板与现有的碳素双极板性能对比表
密度 | 电导率 | 抗弯强度 | 抗拉强度 | |
现有的碳素双极板 | 0.85~1.1 g/cm3 | ≥10 S/cm | ≥20MPa | ≥10MPa |
本发明制成的双极板 | 1.3~2.0g/cm3 | ≥200 S/cm | ≥15MPa | ≥10MPa |
表1说明本发明的双极板与机械强度高但导电性差的现有碳素双极板相比,机械强度上大体相当,但电导率远远高出,密度提高50%以上,说明该工艺可显著增强双极板的导电性。
以上述依据本发明的理想实施例为启示,通过上述的说明内容,相关工作人员完全可以在不偏离本项发明技术思想的范围内,进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容,必须要根据权利要求范围来确定其技术性范围。
Claims (7)
1.一种液流电池双极板制备工艺,其特征是:具有如下过程,
(1)、将可膨胀石墨与导电添加剂的混合物辊压成表面无气泡的石墨预制板;
(2)、将碳纤维布碳化或石墨化处理成碳毡;
(3)、自下而上依次层叠热塑膜、石墨预制板、热塑膜、碳毡、热塑膜、石墨预制板和热塑膜,在加温加压状态下对层叠板进行压制;
(4)、冷却定型成双极板板材,经分切成为液流电池双极板;
过程(3)中对层叠板的加温加压使热塑膜熔融后成为渗入石墨预制板和渗入石墨预制板与碳毡的粘接剂。
2.根据权利要求1所述的液流电池双极板制备工艺,其特征是:过程(1)中的可膨胀石墨与导电添加剂的重量百分比为分别为99.9%~80%和0.1%~20%。
3.根据权利要求1所述的液流电池双极板制备工艺,其特征是: 过程(1)中的导电添加剂中包括碳纳米管、石墨烯、导电炭黑、活性炭和导电纤维中一种或两种或两种以上组合物。
4.根据权利要求1所述的液流电池双极板制备工艺,其特征是:过程(2)中碳纤维布的克重为5~200g/cm2、厚度为20~500μm。
5.根据权利要求1所述的液流电池双极板制备工艺,其特征是:过程(3)中热塑膜为聚丙烯膜、聚乙烯膜、热塑型酚醛膜、聚苯硫醚膜或聚偏氟乙烯膜。
6.根据权利要求1所述的液流电池双极板制备工艺,其特征是:过程(3)中热塑膜厚度为10~400μm。
7.根据权利要求1所述的液流电池双极板制备工艺,其特征是:过程(3)中压机对层叠板的压力为1~50mpa, 层叠板的加热温度为80~350℃,时间为3~120min。
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