CN116396643A - 一种耐酸碱导电涂料复合金属电极板及制备方法 - Google Patents
一种耐酸碱导电涂料复合金属电极板及制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐酸碱导电涂料复合金属电极板及制备方法。所述耐酸碱导电涂料包括以下重量百分比的组分：碳素导电粉体10％‑60％；耐酸碱树脂5‑50％；分散剂5‰‑18％；消泡剂2‰‑5％；增稠剂5‰‑5％；流平剂2‰‑5％；成膜剂2‰‑5％；溶剂余量。在强度和导电性较高的金属板材上通过机加工或模压方式制出流道，再在金属板材上涂覆上述耐酸碱导电涂料，耐强酸导电涂料完全将金属密封，使强酸或强碱性电解液无法渗入涂层中腐蚀金属板。制备得到的复合金属电极板具有高导电性、高强度、厚度较薄、质量较轻、耐强酸强碱，成本较低等优点。
Description
技术领域
本发明涉及新能源技术领域，特别涉及一种耐酸碱导电涂料复合金属电极板及制备方法。
背景技术
目前市面上现有液流电池电极板根据材质划分为两类，一类是石墨电极板，一类是导电塑料电极板。石墨电极板由高强度高导电性的石墨材料经过机加工制备而成；导电塑料电极板制备工艺为：选择导电碳素粉体(高纯石墨粉、碳纳米管粉、石墨烯粉、导电炭黑粉、碳纤维粉或以上几种的混合粉)加入到耐强酸强碱的塑料粒子内(主要为PP或PE塑料)，经过双螺杆造粒机制成导电塑料母粒，再将导电塑料母粒压延制成导电塑料板材，经过机加工制备而成。
现有制备工艺存在以下技术问题：
对于石墨电极板：(1)石墨强度差，运输和装机时容易出现碎裂；(2)为了提高石墨电极板强度，需增加石墨电极板的厚度，增大了电池体积和电池重量，降低了能量密度；(3)精度较高的流道加工成本较高。
对于导电塑料电极板：(1)塑料电极板强度较石墨略高，电极板厚度可较薄，但导电塑料电极板主要材料是PP或者PE，其在加入较多的碳素导电粉体后脆性增大，在运输和装机时仍容易碎裂；(2)由于塑料电极板厚度较薄，且具有一定脆性，在加工流道时容易开裂，因此无法在其上加工流道；(3)导电塑料电极板内阻较大，导致电阻热的产生，造成能量损失。尤其在大电流状态下容易引发热失控，由于PP和PE材质均属于耐温性较差的塑料材料，热失控严重时可使电极板发生形变，引发安全事故；(4)导电塑料电极板制作工艺复杂，生产成本较高。
发明内容
本发明为了解决上述技术问题，提供一种耐酸碱导电涂料复合金属电极板及制备方法。
第一方面，本发明提供一种耐酸碱导电涂料，是采用以下技术方案得以实现的。
一种耐酸碱导电涂料，包括以下重量百分比的组分：
进一步的，所述碳素导电粉体选用石墨粉、碳纳米管粉、石墨烯粉、导电炭黑粉、碳纤维粉中的一种或多种的混合粉。
进一步的，所述耐酸碱树脂选用聚乙烯树脂、聚丙烯树脂、有机氟树脂中的一种或几种混合树脂。
进一步的，所述分散剂选用聚季铵盐类表面活性剂或非离子型高分子表面活性剂。
进一步的，所述消泡剂选用醇类或改性有机硅类消泡剂。
进一步的，所述增稠剂选用非离子型高分子聚合物。
进一步的，所述流平剂选用聚醚改性有机硅高分子聚合物。
进一步的，所述成膜剂选用醇类物质。
第二方面，本发明提供一种耐酸碱导电涂料的制备方法，是采用以下技术方案得以实现的。
一种上述耐酸碱导电涂料的制备方法，包括以下步骤：
a.将规定量的碳素导电粉体分散在溶剂中，并加入分散剂，制成分散液；
b.将所得分散液加入到规定量的耐酸碱树脂中；
c.向步骤b所得混合物中加入规定量的消泡剂、增稠剂、流平剂和成膜剂，充分搅拌，再反复经过挤压得到耐酸碱导电涂料。
第三方面，本发明提供一种复合金属电极板的制备方法，是采用以下技术方案得以实现的。
一种复合金属电极板的制备方法，包括以下步骤：
S1.配置耐酸碱导电涂料：采用上述方法制备得到耐酸碱导电涂料；
S2.制备金属板：选取金属板，在金属板两面制作流道；
S3.将步骤S1制备的耐酸碱导电涂料涂覆在步骤S2的金属板表面，固化后得到复合金属电极板。
进一步的，步骤S2中，金属板的厚度为0.2-2mm。
进一步的，步骤S3中，固化处理条件为：在60-150℃温度下处理10-30min。
第四方面，本发明提供一种复合金属电极板，是采用以下技术方案得以实现的。
一种上述制备方法制备得到的复合金属电极板。
本申请具有以下有益效果。
1.本申请的复合金属电极板由于金属材料的支撑，强度高，在运输和装机时不会出现碎裂问题，便于施工；
2.由于金属板强度高，复合金属电极板的厚度可以较薄，减小了电池体积，降低了电池重量，提升了电池能量密度；
3.由于金属材料的高可塑性和高强度，可在其上制作流道，便于电解液充分均匀的在电极上进行反应；
4.本申请复合金属电极板由于主要由金属构成，内阻较低，因此在电极板上基本不会产生电阻热，基本无能量损失；在大电流状态下不会引发热失控，且即便出现电池温度过高的情况，也会因为金属板强度高，电极板不会发生形变，极大降低了安全事故的出现；
5.本申请复合金属电极板生产成本较低，价格优势明显，综合性价比强。
具体实施方式
下面结合实施例对本发明进行进一步的说明。
一种复合金属电极板的制备方法，包括以下步骤：
(1)调配耐酸碱导电涂料：碳素导电粉体为耐酸碱导电涂料总质量的10-60％，碳素导电粉体选用高纯石墨粉、碳纳米管粉、石墨烯粉、导电炭黑粉、碳纤维粉中的一种或以上几种的混合粉。将碳素导电粉体首先通过搅拌机、卧式砂磨机、篮式砂磨机或其他机械分散设备均匀分散在可以与所选树脂相溶的溶剂中(如果选择砂磨机，则研磨转速为500-5000r/min，时间2h-10h)，制成分散液，在分散过程中加入分散剂。之后，将制备好的分散液加入到所选树脂中(树脂需长期可耐强酸强碱，且在金属板上具有较高附着力，耐强酸碱液高流速冲刷)，最后加入消泡剂、增稠剂、流平剂和成膜剂。经过搅拌设备的充分搅拌，使分散液与树脂充分均匀互溶，再反复经过三辊机挤压，制成耐酸碱导电涂料，耐酸碱导电涂料粘度为100cps-30000cps。
其中，耐酸碱树脂为耐酸碱导电涂料总质量的5％-50％；成膜剂为醇类物质，用量为耐酸碱导电涂料总质量的2‰-5％；分散剂为聚季铵盐类表面活性剂或非离子型高分子表面活性剂，用量为耐酸碱导电涂料总质量的5‰-18％；消泡剂为醇类或改性有机硅类消泡剂，用量为耐酸碱导电涂料总质量的2‰-5％；增稠剂为非离子型高分子聚合物，用量为耐酸碱导电涂料总质量的5‰-5％；流平剂为聚醚改性有机硅高分子聚合物，用量为耐酸碱导电涂料总质量的2‰-5％。
(2)制备金属板：选取具有较高导电性的金属板，厚度为0.2-2mm，材质为铜或铜合金、铝或铝合金、铁、不锈钢或其他易于加工且具有良好导电性的金属材质。经过模压或者雕刻在金属板两面制作流道(根据所选金属材料，为降低成本和导电涂料与金属板之间的接触电阻，可在金属板上镀上接触电阻较小的金属层，如铜、银等低电阻金属)；
(3)涂层树脂：通过喷涂、浸涂、辊涂或刷涂等涂层工艺将耐酸碱导电涂料涂覆在金属板表面，然后经过10-30min，在60-150℃温度下将涂覆在金属板表面的耐酸碱导电涂料固化，使其对金属板进行严格密封。
实施例1
一种复合金属电极板的制备方法，包括以下步骤：
(1)制备涂料用导电剂：以导电剂总量100份计，称取3份分散剂，加入67份去离子水中搅拌均匀，其中分散剂为长链脂肪醇聚氧乙烯醚(AEO-3)，再加入30份由10％碳纳米管粉(嘉兴纳科新材料有限公司SCC-9)和90％导电炭黑粉(嘉兴纳科新材料有限公司TCJ-9)组成的碳素导电碳粉，制备成碳素粉体预分散液，将预分散液放置于卧式砂磨机中，以2000r的转速研磨分散4h，制备成导电剂；
(2)配置耐酸碱导电涂料：以耐酸碱导电涂料100份计，称取步骤(1)制备的导电剂70份，加入25份水性氯化聚丙烯树脂(日本东洋纺E-480T)，再加入消泡剂1份(广东中联邦精细化工B-0518)、增稠剂1份(PEO-8)、水性流平剂1份(BYK-333)和成膜剂2份(丙二醇)。采用真空行星搅拌机充分搅拌，制成粘度600cps的耐酸碱导电涂料。
(2)制备金属板：选取具有较高导电性的金属板，厚度为0.5mm，材质为铝锰合金。经过模压在金属板两面制作流道，流道制作完成后在金属板上进行镀铜，铜镀层的厚度为10μm；
(3)涂层树脂：通过喷涂工艺将耐酸碱导电涂料均匀涂覆在金属板上下表面，然后经过120℃、15min使涂覆在金属板表面的耐酸碱导电涂料固化，涂层干膜厚度为0.1mm。
性能检测
1.涂层附着力需通过测试：测试方式主要是将50mm*100mm*0.6mm涂覆好的金属板固定在PP管道内，分三组，分别用40％的浓硫酸、10％的浓盐酸和20％浓氢氧化钠，在直径在100mm的PP管道中以15L/min流速，在温度40℃温度下，连续冲刷1500小时，再以采用百格测试法对三组金属板上的涂层附着力进行测试，刀齿间距1mm，得出附着力ISO等级≥1级；
2.导电性测试：使用方阻测试仪检测涂层固化后的方块电阻，方阻值≤0.3Ω；经过1500小时，由40％的浓硫酸、10％的浓盐酸和20％浓氢氧化钠冲刷后，方阻值≤0.5Ω；
3.涂层漏点测试：经过1500小时，由40％的浓硫酸、10％的浓盐酸和20％浓氢氧化钠冲刷后，使用2000倍显微镜观察涂层表面，涂层任何位置均无金属层裸露。
本具体实施方式的实施例均为本发明的较佳实施例，并非依此限制本发明的保护范围，故：凡依本发明的结构、形状、原理所做的等效变化，均应涵盖于本发明的保护范围之内。
Claims (8)
1.一种耐酸碱导电涂料，其特征在于：包括以下重量百分比的组分：
2.根据权利要求1所述的一种耐酸碱导电涂料，其特征在于：所述碳素导电粉体选用石墨粉、碳纳米管粉、石墨烯粉、导电炭黑粉、碳纤维粉中的一种或多种的混合粉。
3.根据权利要求1所述的一种耐酸碱导电涂料，其特征在于：所述耐酸碱树脂选用聚乙烯树脂、聚丙烯树脂、有机氟树脂中的一种或几种混合树脂。
4.一种权利要求1-3任一所述耐酸碱导电涂料的制备方法，其特征在于：包括以下步骤：
a.将规定量的碳素导电粉体分散在溶剂中，并加入分散剂，制成分散液；
b.将所得分散液加入到规定量的耐酸碱树脂中；
c.向步骤b所得混合物中加入规定量的消泡剂、增稠剂、流平剂和成膜剂，充分搅拌，再反复经过挤压得到耐酸碱导电涂料。
5.一种复合金属电极板的制备方法，其特征在于：包括以下步骤：
S1.配置耐酸碱导电涂料：采用权利要求4所述方法制备得到耐酸碱导电涂料；
S2.制备金属板：选取金属板，在金属板两面制作流道；
S3.将步骤S1制备的耐酸碱导电涂料涂覆在步骤S2的金属板表面，固化后得到复合金属电极板。
6.根据权利要求5所述的一种复合金属电极板的制备方法，其特征在于：步骤S2中，金属板的厚度为0.2-2mm。
7.根据权利要求5所述的一种复合金属电极板的制备方法，其特征在于：步骤S3中，固化处理条件为：在60-150℃温度下处理10-30min。
8.一种权利要求5-7任一所述制备方法制备得到的复合金属电极板。
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| CN102483977A (zh) * | 2009-08-27 | 2012-05-30 | 大日精化工业株式会社 | 水系碳填料分散涂装液、导电性赋予材料、蓄电装置用电极板、蓄电装置用电极板的制造方法及蓄电装置 |
| CN109524682A (zh) * | 2018-11-12 | 2019-03-26 | 临沂市产品质量监督检验所 | 一种全钒液流电池用金属复合双极板及其制备方法 |
| CN115572508A (zh) * | 2022-10-25 | 2023-01-06 | 嘉兴纳科新材料有限公司 | 一种水性耐强酸环保导电涂料及其制备方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102483977A (zh) * | 2009-08-27 | 2012-05-30 | 大日精化工业株式会社 | 水系碳填料分散涂装液、导电性赋予材料、蓄电装置用电极板、蓄电装置用电极板的制造方法及蓄电装置 |
| CN109524682A (zh) * | 2018-11-12 | 2019-03-26 | 临沂市产品质量监督检验所 | 一种全钒液流电池用金属复合双极板及其制备方法 |
| CN115572508A (zh) * | 2022-10-25 | 2023-01-06 | 嘉兴纳科新材料有限公司 | 一种水性耐强酸环保导电涂料及其制备方法 |
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