CN111978577A - 一种双极板用连续导电纤维毡预浸料及制备方法 - Google Patents
一种双极板用连续导电纤维毡预浸料及制备方法 Download PDFInfo
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Abstract
本发明提供了一种双极板用连续导电纤维毡预浸料及制备方法,将连续导电纤维毡浸渍导电树脂基体形成连续的预浸片材,并用于双极板制备,其组分主要由树脂、增强纤维毡、导电填料及功能助剂组成,其中所述的树脂含量占20wt~45wt%,所述导电填料占55wt~80wt%,所述的功能助剂占2‑6%。采用的方法中导电纤维毡作为双极板骨架结构形成了完整的导电网络,可增强复合材料强度及电导率,解决目前常用复合材料双极板兼具高电导率、高强度、高气密性的技术难题。由预浸料片材制备双极板具有操作工艺简单,成品具有良好的平整度,尺寸公差可控,同时兼具高导电、高强度的性能。
Description
技术领域
本发明涉及氢燃料电池应用领域,提供了一种导电纤维毡预浸料及制备方法,可一步法热压成型制备双极板。
背景技术
氢能作为一种可储、可电、可燃烧的清洁能源,是世界能源转型的一个重大战略方向。氢能在世界范围内备受关注,氢能已经纳入我国能源战略,成为我国优化能源消费结构和保障国家能源供应安全的战略选择。我国已在氢能领域取得了多方面的进展,在国防领域,我国早已试验成功的氢弹就是利用了氢的热核反应释放出的核能,是氢能的一种特殊应用。在航天领域使用以液氢为燃料的液体火箭,是氢用作为燃料能源的典型例子。在宇航研究中氢能具有广阔的应用前景,如火箭发动机、氢内燃机等。在民用工业领域,燃料电池近年来也发展迅速。进入2019年,氢能产业发展速度显着加快,各地方的氢能扶持政策、氢能产业园区如雨后春笋般涌现。
氢燃料电池(Fuel Cell,FC)技术因其具有的高效能、低污染、能源安全等特点近年来得到了各国政府、各大公司以及各研究机构的普遍重视。中国氢能联盟发布《中国氢能源及燃料电池产业白皮书》预测,2020年至2025年间,我国氢能产业产值将达到1万亿元,氢能源车数量达到5万辆。氢燃料电池是燃料电池车的核心动力源,双极板又是燃料电池的核心材料,约占燃料电池成本的24%。双极板也称做集电器,它具有收集电流、疏导反应气体及分隔氧化剂与还原剂的作用;双极板的性能取决于材料特性、流场设计与加工技术。目前氢燃料电池中普遍采用的是石墨双极板和金属双极板。在氢燃料电池环境下,石墨的耐腐蚀性能最好,电导率也高,但成本昂贵,约占电池成本的50%~60%。金属双极板具有高的电导率和好的力学强度,但耐腐蚀方面成了难题。这就导致国内外众研究机构和企业关注并研究碳纤维复合材料双极板,该项技术兼具石墨材料的耐腐蚀性和金属材料的高强度特性,被誉为未来氢燃料电池得以推广应用的第三代核心技术。目前采用BMC成型工艺制备的复合材料双极板已成功应用于氢燃料电池,但导电性差、机械强度低、加工尺寸稳定性差,这些性能有待进一步提高。
发明内容
本发明提供了一种双极板用连续导电纤维毡预浸料及制备方法,解决目前常用复合材料双极板兼具高电导率、高强度、高气密性的技术难题。由预浸料片材制备双极板具有操作工艺简单,同时兼具高导电、高强度的性能。
为了解决上述技术问题,本发明采用的技术方案是:
一种双极板用导电纤维毡预浸料及制备方法,其特征在于将连续导电纤维毡浸渍导电树脂基体形成连续的预浸片材,并用于双极板制备,其组分主要由树脂、增强纤维毡、导电填料及功能助剂组成。
所述的一种双极板用导电纤维毡预浸料,其特征在于连续导电纤维毡主要为:沥青基短切碳纤维毡、聚丙烯腈基碳纤维毡、玻纤/碳纤复合纤维毡、金属纤维/碳纤复合毡、金属纤维/玻纤复合毡、经导电改性的玻璃纤维毡、经导电改性的玄武岩纤维毡中的一种或几种组成,纤维长度为3-5cm,纤维直径为6-12um。
所述的一种双极板用导电纤维毡预浸料,其特征在于树脂基体为酚醛树脂、环氧树脂、呋喃树脂、不饱和聚酯、乙烯基树脂等。热固性树脂基体经热塑性树脂聚偏氟乙烯(PVDF)、聚苯硫醚(PPS)、聚醚酰亚胺(PEI)、聚醚砜(PES)、聚吡咯烷酮、聚醚酮、聚芳砜等热塑性树脂改性。
所述的一种双极板用导电纤维毡预浸料,其特征在于导电填料可为:石墨粉(天然鳞片石墨、球形石墨、膨胀石墨、人造石墨)、碳纤维(CF)、乙炔黑(AB)、碳纳米管(CNT)、炭黑(CB)、石墨烯或经金属改性的镍包石墨粉、镍包碳纤维、镍包碳纳米管等。
所述的一种双极板用导电纤维毡预浸料,其特征在于功能助剂主要为导电填料界面改性剂、分散剂等。
所述的一种双极板用导电纤维毡预浸料,其特征在于:所述的树脂含量占20wt~45wt%,所述导电填料占55wt-80wt%,所述的功能助剂占2-6%。
一种双极板用导电纤维毡预浸料,主要步骤如下:1)按配比称取导电填料用高速剪搅拌机强力搅拌分散5min,搅拌速度4000~12000转/分钟,然后按配比加入功能助剂继续搅拌10min。2)将搅拌分散均匀的粉料及树脂按配比加入捏合机或行星式搅拌机中进一步混合,捏合温度小于65℃,混合45min;3)将分散好的树脂浆料用涂胶机采用热熔法涂膜或刮成层状料,控制胶膜面密度±10g;4)将胶膜在预浸机上与连续导电纤维毡复合,保证与导电纤维毡浸润。
本发明导电纤维毡预浸料可用于与双极板制备,根据双极板尺寸裁成需要的形状可直接一步法热压成型制备双极板。
与现有技术相比,本发明提供的石墨烯改性碳纤维发热膜及制备方法具有以下有益效果:
(1)传统复合材料双极板基本采用BMC工艺,增强纤维及导电填料粒度小,长径比小,形成的导电网络接触电阻大,一定程度影响了双极板导电性能和强度。本发明提供一种新型的导电纤维毡/树脂复合材料,导电纤维毡作为双极板骨架结构形成了完整的导电网络,可增强复合材料强度及电导率。由厚度均匀的片材在成型加工,具有良好的平整度,尺寸公差可控。
(2)本发明采用了金属镀层强化导电性能的的碳质材料,与传统的导电填料相比,在适当降低导电填料的同时提高了双极板制品的电导率,解决了双极板材料兼具高导电、高强度、易成型、高气密性的技术难题。采用导电纤维毡预浸片制备双极板方法,该方法简单易行,适用于批量生产。
附图说明
下面结合附图对本发明的具体实施方式作进一步详细说明。
图1为导电纤维毡预浸料加工双极板流程图。
具体实施方式
本发明提出一种双极板用连续导电纤维毡预浸料制备方法,将连续导电纤维毡用具备导电功能的树脂基体浸渍,可直接用于双极板模压成型。研制出一种新型轻质、高导电、高强度、耐腐蚀满足工程化应用的复合材料双极板。本发明涉及一种双极板用导电纤维毡预浸料,其特征在于,将连续导电纤维毡浸渍导电树脂基体形成连续的预浸片材,按双极板尺寸大小裁剪后可直接压制成型,其组分包括树脂、增强纤维毡、导电填料及功能助剂。连续导电纤维毡由沥青基短切碳纤维毡、聚丙烯腈基碳纤维毡、玻纤/碳纤复合纤维毡、金属纤维/碳纤复合毡、金属纤维/玻纤复合毡、经导电改性的玻璃纤维毡、经导电改性的玄武岩纤维毡中的一种或几种组成,纤维长度为3-5cm,纤维直径为6-12um,纤维面密度200-300g/m2。导电树脂基体为酚醛树脂、环氧树脂、呋喃树脂、不饱和聚酯、乙烯基树脂。热固性树脂基体经热塑性树脂聚偏氟乙烯、聚苯硫醚、聚醚酰亚胺、聚醚砜、聚吡咯烷酮、聚醚酮、聚芳砜等热塑性树脂改性中的一种。导电填料为:石墨粉、碳纤维、乙炔黑、碳纳米管、炭黑、石墨烯或经金属改性的镍包石墨粉、镍包碳纤维、镍包碳纳米管中的几种或一种。功能助剂为导电填料界面改性剂或分散剂。所述的树脂含量占20wt~45wt%,所述导电填料占55wt-80wt%,所述的功能助剂占2-6%。
一种双极板用导电纤维毡预浸料,所述导电纤维毡预浸料用于双极板制备,根据双极板尺寸裁成需要的形状,直接一步法热压成型制备双极板。导电纤维毡预浸料采用热熔二步法制备,步骤如下:(1)按配比称取导电填料用高速剪搅拌机强力搅拌分散5min,搅拌速度4000-12000转/分钟,然后按配比加入功能助剂继续搅拌10min;(2)将搅拌分散均匀的粉料及树脂按配比加入捏合机或行星式搅拌机中进一步混合,捏合温度小于65℃,混合45min;(3)将分散好的树脂浆料用涂胶机采用热熔法涂膜或刮成层状料,控制胶膜面密度±10g;(4)在预浸机将胶膜与连续导电纤维毡复合,保证与导电纤维毡浸润。
下面结合具体实施例对本发明进行进一步描述,但是本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限制本发明的范围。实施例中未注明具体条件者,按照常规提交或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
本发明中的技术及其具体制备方法是按以下步骤进行:
1)按配比称取导电填料用高速剪搅拌机强力搅拌分散5min,搅拌速度4000~12000转/分钟,然后按配比加入功能助剂继续搅拌10min。
2)将搅拌分散均匀的粉料及树脂按配比加入捏合机或行星式搅拌机中进一步混合,捏合温度小于65℃,混合45min;
3)将分散好的树脂浆料用涂胶机采用热熔法涂膜或刮成层状料,控制胶膜面密度±10g;
4)将胶膜在预浸机上与连续导电纤维毡复合,保证与导电纤维毡浸润;
5)将连续的导电碳纤维预浸料按需求裁成需要的尺寸大小直接在压机压制成型。
由上述方法制成的连续纤维毡预浸料,导电纤维毡作为双极板骨架结构形成了完整的导电网络,可增强复合材料强度及电导率。同时由于厚度均匀的片材在成型加工时具有良好的平整度,尺寸公差可控。
实施例1
导电石墨粉:导电炭黑:石墨纤维导电粉=87.5:2.5:10按配比称取5kg,在高速剪搅拌机强力搅拌分散5min,搅拌速度5000转/分钟,然后按粉料重量5%加入分散剂继续搅拌40min;将搅拌分散均匀的粉料与酚醛环氧树脂(树脂基体中含8%的双氰胺固化剂,4%的有机脲促进剂,10%的聚醚酰亚胺增韧剂)按质量比1:1加入捏合机中进一步混合,捏合温度小于65℃,混合45min;将分散好的树脂浆料用涂胶机采用热熔法涂膜,涂胶温度70±3℃,控制胶膜面密度80±10g;采用面密度100±10g为连续导电纤维毡在预浸机将胶膜复合,预浸温度90±3℃,保证与导电纤维毡浸润。采用该预浸片压制双极板,树脂基体占20%,导电填料及纤维占80%。
Claims (8)
1.一种双极板用导电纤维毡预浸料,其特征在于,将连续导电纤维毡浸渍导电树脂基体形成连续的预浸片材,按双极板尺寸大小裁剪后可直接压制成型,其组分包括树脂、增强纤维毡、导电填料及功能助剂。
2.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于,连续导电纤维毡由沥青基短切碳纤维毡、聚丙烯腈基碳纤维毡、玻纤/碳纤复合纤维毡、金属纤维/碳纤复合毡、金属纤维/玻纤复合毡、经导电改性的玻璃纤维毡、经导电改性的玄武岩纤维毡中的一种或几种组成,纤维长度为3-5cm,纤维直径为6-12um,纤维面密度200-300g/m2。
3.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于,导电树脂基体为酚醛树脂、环氧树脂、呋喃树脂、不饱和聚酯、乙烯基树脂。热固性树脂基体经热塑性树脂聚偏氟乙烯、聚苯硫醚、聚醚酰亚胺、聚醚砜、聚吡咯烷酮、聚醚酮、聚芳砜等热塑性树脂改性中的一种。
4.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于,导电填料为:石墨粉、碳纤维、乙炔黑、碳纳米管、炭黑、石墨烯或经金属改性的镍包石墨粉、镍包碳纤维、镍包碳纳米管中的几种或一种。
5.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于,功能助剂为导电填料界面改性剂或分散剂。
6.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于:所述的树脂含量占20wt~45wt%,所述导电填料占55wt-80wt%,所述的功能助剂占2-6%。
7.根据权利要求1所述的一种双极板用导电纤维毡预浸料,其特征在于:
所述导电纤维毡预浸料用于双极板制备,根据双极板尺寸裁成需要的形状,直接一步法热压成型制备双极板。
8.根据权利要求1所述的一种双极板用导电纤维毡预浸料的制备方法,其特征在于,导电纤维毡预浸料采用热熔二步法制备,步骤如下:
(1)按配比称取导电填料用高速剪搅拌机强力搅拌分散5min,搅拌速度4000-12000转/分钟,然后按配比加入功能助剂继续搅拌10min;
(2)将搅拌分散均匀的粉料及树脂按配比加入捏合机或行星式搅拌机中进一步混合,捏合温度小于65℃,混合45min;
(3)将分散好的树脂浆料用涂胶机采用热熔法涂膜或刮成层状料,控制胶膜面密度±10g;
(4)在预浸机将胶膜与连续导电纤维毡复合,保证与导电纤维毡浸润。
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