CN115447215A - 导电片材的制备方法、导电片材及新型液流电池双极板 - Google Patents

导电片材的制备方法、导电片材及新型液流电池双极板 Download PDF

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CN115447215A
CN115447215A CN202210895419.2A CN202210895419A CN115447215A CN 115447215 A CN115447215 A CN 115447215A CN 202210895419 A CN202210895419 A CN 202210895419A CN 115447215 A CN115447215 A CN 115447215A
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conductive sheet
carbon
hot
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朱洪模
曾志军
马佳钰
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Beijing Guodian Ruixin Technology Co ltd
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Abstract

本申请公开了一种导电片材的制备方法、导电片材及新型液流电池双极板，基于本实施例的实施，本申请具备以下特点：1)上下两侧由于加入了石墨毡/碳纸/碳纤维布，大大提高了双极板片材的导电性，从而降低了表面电阻，使这种导电碳塑片材双极板的表面接触电阻与石墨片材双极板表面的接触电阻相当，甚至优于石墨片材双极板；2)中间层仍为碳塑导电片材，虽然电阻率略高，但由于中间层厚度很薄，因此对本体电阻影响很小；同时中间层的存在起到了增加韧性和强度，同时对气液阻断的作用。既具备了石墨片材的高导电特性，同时兼具了碳塑导电片材的韧性及阻隔性，在全钒/铁铬液流电池中使用具有显著的优点。

Description

导电片材的制备方法、导电片材及新型液流电池双极板
技术领域
本申请涉及液流电池技术领域，具体而言，涉及一种导电片材的制备方法、导电片材、新型液流电池双极板和液流电池。
背景技术
为实现“双碳”目标，新能源发电的装机量日益增加。新能源发电的间歇性和波动性对电网稳定可靠运行带来了比较大的冲击。大规模储能技术是解决该问题的重要手段之一，其中液流电池储能技术是大规模长时储能系统的代表技术。液流电池是一种导电片材的制备方法新型蓄电储能设备，一般具有寿命长，环境友好，安全性高等优点，主要应用于电网调峰、风能和太阳能等可再生能源发电等领域，可提高电网稳定性，保障电网安全。目前液流电池主要包括全钒液流电池、锌溴液流电池、铁铬液流电池、锌锰液流电池、锌空气液流电池等。
传统的液流电池双极板材料多采用石墨片材或碳塑导电片材。其中：(1)石墨片材包括模压石墨、柔性石墨板等，石墨片材的电阻率较低，但本身韧性及密封性不良，严重影响后期工艺，同时制备成本较高，使用受到一定限制。同时，石墨压板的气液阻隔性不良，长时间运行会导致电池自放电加速，严重情况下影响电池寿命。(2)碳塑导电片材由高分子树脂材料+碳系导电材料如炭黑，石墨等组成，在韧性方面可以做到较好，但受到加工工艺的限制，碳含量添加不能太高，因此电阻率会比较高，从而影响电池的电压效率。
经分析表明，双极板材料电阻率对电池电阻的影响主要包括两个方面，一是由于片材的本身电阻影响，材料欧姆电阻在充放电过程中造成电压的损耗，降低电池的电压效率；二是由于表面接触电阻的影响，由于在全钒液流电池或铁铬液流电池中，采用石墨毡作为电极，石墨毡电极会压接到双极板表面，从而形成电子通路，因此在电极和双极板界面的接触电阻也会对电池内阻造成影响，而且接触电阻带来的电压损耗远高于材料本身电阻带来的电压损耗。
发明内容
本申请的主要目的在于提供一种导电片材的制备方法、导电片材、新型液流电池双极板和液流电池，以解决目前的问题。
为了实现上述目的，本申请提供了如下技术：
本申请第一方面，提供一种导电片材的制备方法，包括如下制备步骤：
制备中间层，将所述中间层作为基材；
制备高导电层，将所述高导电层叠放于所述中间层上；
预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材。
作为本申请的一种可选实施方案，可选地，所述制备中间层，包括：
准备高分子树脂材料和碳塑导电片材料；
将所述高分子树脂材料和碳塑导电片材料混合，并进行热熔混炼挤出，得到碳塑导电片材；
将所述碳塑导电片材进行加工预处理，得到所述中间层；
其中，所述中间层工艺性能要求需满足：厚度0.5-2.5mm，电阻率2-10Ω.mm，拉伸强度≥15MPa。
作为本申请的一种可选实施方案，可选地，所述高分子树脂材料为聚乙烯、聚丙烯或聚氯乙烯中的至少一种。
作为本申请的一种可选实施方案，可选地，所述碳系导电材料为石墨、炭黑、碳纳米管或石墨烯中的至少一种。
作为本申请的一种可选实施方案，可选地，在添加的所述高分子树脂材料和碳塑导电片材料中，所述碳系导电材料添加含量百分比为40％-65％。
作为本申请的一种可选实施方案，可选地，所述制备高导电层，将所述高导电层叠放置于所述中间层上，包括：
制备两片高导电层；
按照高导电层-中间层-高导电层的叠放顺序，将两片高导电层叠放在所述中间层的两侧面上，准备热压；
其中：
所述高导电层为石墨毡、碳纤维布或碳纸中的至少一种；
所述高导电层的厚度为0.3-2.5mm。
作为本申请的一种可选实施方案，可选地，所述预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材，包括：
根据预设制备尺寸，准备热压模具，并将叠放的所述高导电层和所述中间层置于所述热压模具中；
配置真空热压机，并设定热压工艺参数，并将所述热压模具放置于所述真空热压机中，进行热压，得到所述导电片材；
冷却、取模，取出所述导电片材；
其中，所述热压工艺参数：
热压温度140～170℃；
热压压力40～60kg/cm2，
热压时间200～300s，
冷却压力40～60kg/cm2，
冷却温度25℃，
冷却压力40～60kg/cm2，
冷却时间200～300s。
本申请第二方面，提供一种导电片材，所述导电片材根据上述所述的导电片材的制备方法制备得到。
本申请第三方面，提供一种新型液流电池双极板，所述新型液流电池双极板包括上述所述的导电片材。
本申请第四方面，提供一种液流电池，所述液流电池包括上述所述的新型液流电池双极板。
与现有技术相比较，本申请能够带来如下技术效果：
1、基于本实施例的实施，本申请提供一种新型的用于液流电池双极板材料，尤其是用于全钒液流电池及铁铬液流电池双极板的制备方法；采用这种方法制备的双极板材料具备以下特点：
1)上下两侧由于加入了石墨毡/碳纸/碳纤维布，大大提高了双极板片材的导电性，从而降低了表面电阻，使这种导电碳塑片材双极板的表面接触电阻与石墨片材双极板表面的接触电阻相当，甚至优于石墨片材双极板；
2)中间层仍为碳塑导电片材，虽然电阻率略高，但由于中间层厚度很薄，因此对本体电阻影响很小；同时中间层的存在起到了增加韧性和强度，同时对气液阻断的作用。
2、采用这种方法制备的高导电双极板材料既具备了石墨片材的高导电特性，同时兼具了碳塑导电片材的韧性及阻隔性，在全钒/铁铬液流电池中使用具有显著的优点。
附图说明
构成本申请的一部分的附图用来提供对本申请的进一步理解，使得本申请的其它特征、目的和优点变得更明显。本申请的示意性实施例附图及其说明用于解释本申请，并不构成对本申请的不当限定。在附图中：
图1是本发明导电片材的制备方法的制备流程示意图；
图2是本发明导电片材的结构示意图。
具体实施方式
为了使本技术领域的人员更好地理解本申请方案，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分的实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本申请保护的范围。
需要说明的是，本申请的说明书和权利要求书及上述附图中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的数据在适当情况下可以互换，以便这里描述的本申请的实施例。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。
在本申请中，术语“上”、“下”、“左”、“右”、“前”、“后”、“顶”、“底”、“内”、“外”、“中”、“竖直”、“水平”、“横向”、“纵向”等指示的方位或位置关系为基于附图所示的方位或位置关系。这些术语主要是为了更好地描述本申请及其实施例，并非用于限定所指示的装置、元件或组成部分必须具有特定方位，或以特定方位进行构造和操作。
并且，上述部分术语除了可以用于表示方位或位置关系以外，还可能用于表示其他含义，例如术语“上”在某些情况下也可能用于表示某种依附关系或连接关系。对于本领域普通技术人员而言，可以根据具体情况理解这些术语在本申请中的具体含义。
另外，术语“多个”的含义应为两个以及两个以上。本实施例中，各个片材层的数量和贴合面，可以不仅仅限于两面，可以根据情况设置多层，具体根据电池的设计要求或者用户定制即可满足。
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本申请。
实施例1
如图1所示，本申请第一方面，提供一种导电片材的制备方法，包括如下制备步骤：
1、制备中间层，将所述中间层作为基材；
作为制备液流电池双极板的导电片材，其为层状结构，为了增加韧性和强度，同时对气液阻断，首先需要制备基材即中间层。本实施例，中间层仍为碳塑导电片材，虽然电阻率略高，但由于中间层厚度很薄，因此对本体电阻影响很小；同时中间层的存在起到了增加韧性和强度，同时对气液阻断的作用。
2、制备高导电层，将所述高导电层叠放于所述中间层上；
基材制备完毕，在基材的表面压合上导电层。本实施例，在中间层的上下两侧由于加入了高导电层(石墨毡/碳纸/碳纤维布)，大大提高了双极板片材的导电性，从而降低了表面电阻，使这种导电碳塑片材双极板的表面接触电阻与石墨片材双极板表面的接触电阻相当，甚至优于石墨片材双极板。
3、预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材。
材料制备完毕，根据热压工艺，将所述高导电层和所述中间层叠放布置在热压模具中，尽心热压、冷却、脱模，得到该导电片材。
下面将具体描述各个制备步骤的实现方法。
作为本申请的一种可选实施方案，可选地，所述制备中间层，包括：
准备高分子树脂材料和碳塑导电片材料；
将所述高分子树脂材料和碳塑导电片材料混合，并进行热熔混炼挤出，得到碳塑导电片材；
将所述碳塑导电片材进行加工预处理，得到所述中间层；
其中，所述中间层工艺性能要求需满足：厚度0.5-2.5mm，电阻率2-10Ω.mm，拉伸强度≥15MPa。
作为本申请的一种可选实施方案，可选地，所述高分子树脂材料为聚乙烯、聚丙烯或聚氯乙烯中的至少一种。
作为本申请的一种可选实施方案，可选地，所述碳系导电材料为石墨、炭黑、碳纳米管或石墨烯中的至少一种。
作为本申请的一种可选实施方案，可选地，在添加的所述高分子树脂材料和碳塑导电片材料中，所述碳系导电材料添加含量百分比为40％-65％。
首先采用挤出成型的方式，将高分子树脂材料与碳系导电材料组成的混合原料进行热熔混炼挤出；
然后通过压延，冷却，牵引裁切等工艺获得碳塑导电片材。
其中高分子树脂材料包括但不仅限于聚乙烯、聚丙烯、聚氯乙烯等；碳系导电材料包括但不仅限于石墨、炭黑、碳纳米管、石墨烯等，碳系导电材料添加含量40％-65％；制得的导电塑料片材厚度0.5mm到2.5mm，电阻率2-10Ω.mm、拉伸强度≥15MPa。
本实施例，高分子树脂材料和碳系导电材料的配比成分比，本实施例不做限制，但是碳系导电材料的添加含量需要满足占比40％-65％。高分子树脂材料和碳系导电材料的具体选材，本实施例不做限定，能够从上述提供的材料中选择或者可以由替代的材料皆可用来制备。
在热熔混炼挤出、压延(0.5mm到2.5mm厚)，冷却，牵引裁切等工艺中，所采用的设备以及工艺参数，本实施例不限制。
制作得到中间层后，即得到0.5mm到2.5mm厚的导电塑料片材，进行牵引裁切等预处理，得到符合预设规格尺寸的片状中间层。
其次，准备高导电层。
本实施，以制备的碳塑导电片材为基材(实际上为具备尺寸规格的中间层)，同时准备两片石墨毡、碳纸或碳纤维布，其中石墨毡、碳纤维布、碳纸的厚度为0.3mm-2.5mm，根据双极板的尺寸规格准备相应的热压模具，然后将石墨毡/碳纸/碳纤维布及导电塑料片材依次叠放到热压模具中。
作为本申请的一种可选实施方案，可选地，所述制备高导电层，将所述高导电层叠放置于所述中间层上，包括：
制备两片高导电层；
按照高导电层-中间层-高导电层的叠放顺序，将两片高导电层叠放在所述中间层的两侧面上，准备热压；
其中：
所述高导电层为石墨毡、碳纤维布或碳纸中的至少一种；
所述高导电层的厚度为0.3-2.5mm。
作为本申请的一种可选实施方案，可选地，所述预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材，包括：
根据预设制备尺寸，准备热压模具，并将叠放的所述高导电层和所述中间层置于所述热压模具中；
配置真空热压机，并设定热压工艺参数，并将所述热压模具放置于所述真空热压机中，进行热压，得到所述导电片材；
冷却、取模，取出所述导电片材；
其中，所述热压工艺参数：
热压温度140～170℃；
热压压力40～60kg/cm2，
热压时间200～300s，
冷却压力40～60kg/cm2，
冷却温度25℃，
冷却压力40～60kg/cm2，
冷却时间200～300s。
将热压模具放置于真空热压机中，进行热压，将石墨毡/碳纸/碳纤维布完全压入到碳塑导电片材中，形成一体；然后待模具冷却后，将压制完成的一体化碳塑导电片材从模具中取出。
本实施例，高导电层为石墨毡、碳纤维布或碳纸中的一种，厚度为0.3mm-2.5mm。在其他实施方案中，只要可与石墨毡、碳纤维布或碳纸相替换的高导电层，皆可以用于本申请的制备。
本实施例，优选在中间层两侧面各设置一层高导电层。但是在其他的实施方案中，可以一侧设置，也可以在每侧设置一层以上的材料等，具体根据用户选择和电池设计制作需求决定即可。
实施例2
基于实施例1的制备方案，本实施得到一种导电片材。
本申请第二方面，提供一种导电片材，所述导电片材根据上述所述的导电片材的制备方法制备得到。
导电片材的结构和结构参数，具体参见实施例1，本实施例不做赘述。
实施例3
本申请第三方面，提供一种新型液流电池双极板，所述新型液流电池双极板包括上述所述的导电片材。
本实施例将制备得到的导电片材作为一种新型液流电池双极板的制备材料，将其用于新型液流电池双极板的制备。
导电片材的形状和尺寸等，根据制备新型液流电池双极板的设计要求进行制备、加工即可。
实施例4
本申请第四方面，提供一种液流电池，所述液流电池包括上述所述的新型液流电池双极板。
基于上述实施例，本实施例还提供一种液流电池，该液流电池采用的是由本申请导电片层制备得到的新型液流电池双极板。
上述液流电池的加工、制备工艺，为本行业技术人员的加工工艺，本实施例不做限制。
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (10)

1.一种导电片材的制备方法，其特征在于，包括如下制备步骤：
制备中间层，将所述中间层作为基材；
制备高导电层，将所述高导电层叠放于所述中间层上；
预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材。
2.如权利要求1所述的导电片材的制备方法，其特征在于，所述制备中间层，包括：
准备高分子树脂材料和碳塑导电片材料；
将所述高分子树脂材料和碳塑导电片材料混合，并进行热熔混炼挤出，得到碳塑导电片材；
将所述碳塑导电片材进行加工预处理，得到所述中间层；
其中，所述中间层工艺性能要求需满足：厚度0.5-2.5mm，电阻率2-10Ω.mm，拉伸强度≥15MPa。
3.如权利要求2所述的导电片材的制备方法，其特征在于，所述高分子树脂材料为聚乙烯、聚丙烯或聚氯乙烯中的至少一种。
4.如权利要求2所述的导电片材的制备方法，其特征在于，所述碳系导电材料为石墨、炭黑、碳纳米管或石墨烯中的至少一种。
5.如权利要求2所述的导电片材的制备方法，其特征在于，在添加的所述高分子树脂材料和碳塑导电片材料中，所述碳系导电材料添加含量百分比为40％-65％。
6.如权利要求1所述的导电片材的制备方法，其特征在于，所述制备高导电层，将所述高导电层叠放置于所述中间层上，包括：
制备两片高导电层；
按照高导电层-中间层-高导电层的叠放顺序，将两片高导电层叠放在所述中间层的两侧面上，准备热压；
其中：
所述高导电层为石墨毡、碳纤维布或碳纸中的至少一种；
所述高导电层的厚度为0.3-2.5mm。
7.如权利要求6所述的导电片材的制备方法，其特征在于，所述预置热压环境，将叠放的所述高导电层和所述中间层置于所述热压环境中进行热压，得到制备液流电池的导电片材，包括：
根据预设制备尺寸，准备热压模具，并将叠放的所述高导电层和所述中间层置于所述热压模具中；
配置真空热压机，并设定热压工艺参数，并将所述热压模具放置于所述真空热压机中，进行热压，得到所述导电片材；
冷却、取模，取出所述导电片材；
其中，所述热压工艺参数：
热压温度140～170℃；
热压压力40～60kg/cm2，
热压时间200～300s，
冷却压力40～60kg/cm2，
冷却温度25℃，
冷却压力40～60kg/cm2，
冷却时间200～300s。
8.一种导电片材，其特征在于，所述导电片材根据权利要求1-7中任一项所述的导电片材的制备方法制备得到。
9.一种新型液流电池双极板，其特征在于，所述新型液流电池双极板包括权利要求8所述的导电片材。
10.一种液流电池，其特征在于，所述液流电池包括权利要求9所述的新型液流电池双极板。
CN202210895419.2A 2022-07-26 2022-07-26 导电片材的制备方法、导电片材及新型液流电池双极板 Pending CN115447215A (zh)

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