CN107858857A - 一种高导电复合纸及其制备方法 - Google Patents

一种高导电复合纸及其制备方法 Download PDF

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CN107858857A
CN107858857A CN201710984702.1A CN201710984702A CN107858857A CN 107858857 A CN107858857 A CN 107858857A CN 201710984702 A CN201710984702 A CN 201710984702A CN 107858857 A CN107858857 A CN 107858857A
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polyaniline
zinc oxide
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extrusion coating
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CN107858857B (zh
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陈庆
司文彬
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He Zhenfang
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Chengdu New Keli Chemical Science Co Ltd
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Abstract

本发明提供一种高导电复合纸及其制备方法，利用超声技术，使纳米氧化锌粒子均匀分散在聚苯胺当中，使得聚苯胺生长在碳纳米管的表面，并且将纳米碳管完全包覆在内，制备出一种碳纳米管/聚苯胺/氧化锌三相复合导电材料作为抄纸原料，将复合导电原料应用于抄纸过程中制备出一种高导电复合纸，本发明提供上述方法不但克服了在制备聚苯胺纤维与碳纳米管复合纸材料时聚苯胺的团聚问题的技术缺陷，还可以使纳米氧化锌粒子均匀的分散在聚苯胺结构当中，有效的提高了聚苯胺的导电性能和稳定性，制备的复合纸具有优异的导电性。

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一种高导电复合纸及其制备方法
技术领域
本发明涉及造纸技术领域，具体涉及一种高导电复合纸及其制备方法。
背景技术
复合纸是相对于普通纸而言的一类具有特殊用途的纸张的统称。复合加工纸不仅能改善纸和纸板的外观性能和强度，主要的是提高防水，防潮，耐油，气密保香等性能，同时还会获得热封性，阻光性，耐热性等。复合纸已广泛用于轻工、纺织、食品、水利、电力、电信、交通和建筑等行业，普通纸的原料多为植物纤维，复合纸的原料除了植物纤维以外，还配有合成纤维等原料来弥补天然纤维的某些弱点。
聚苯胺，高分子化合物的一种，具有特殊的电学、光学性质，经掺杂后可具有导电性及电化学性能。经一定处理后，可制得各种具有特殊功能的设备和材料，如可作为生物或化学传感器的尿素酶传感器、电子场发射源、较传统锂电极材料在充放电过程中具有更优异的可逆性的电极材料、选择性膜材料、防静电和电磁屏蔽材料、导电纤维、防腐材料，等等。聚苯胺因其具有的原料易得、合成工艺简单、化学及环境稳定性好等特点而得到了广泛的研究和应用。
碳是世界上含量及广的一种元素，碳材料在人类发展史上起着主导的行的作用。碳材料几乎包括了地球上所有物质所具有的性质，如最硬--最软、绝缘体--半导体--超导体、绝热-良导热、吸光--全透光。随着时代的变迁和科学的进步，人们不断地发现和利用碳，人们对碳元素的开发具有无限的可能性。
中国专利公开号101003956公开了一种复合导电碳纤维纸，用丙烯腈基碳纤维和其它碳素材料作为原料,采用聚苯胺与常规的聚乙烯醇、水溶性酚醛树脂混合后作为粘合剂，以及海藻酸钠与常规分散剂混合使用。用常规湿法造纸技术进行造纸,再将得到的碳纸进行真空干燥，然后用5%-20%聚四氟乙烯乳液处理后，最后在通入氮气的情况下进行碳化,碳化温度不低于1000℃，可得复合碳纤维纸。该复合碳纤维纸主要应用于燃料电池方面。
中国专利公开号102815043 B公开了一种石墨烯/聚苯胺复合纸的制备方法，包括以下步骤：提供氧化石墨烯的分散液；将所述氧化石墨烯分散液与还原剂混合以得到浆料，然后将所述浆料涂覆在衬底上，接着进行烘干以得到石墨烯纸；以及通过将聚苯胺沉积在所述石墨烯纸上而得到石墨烯/聚苯胺复合纸。本发明的优点在于利用简单操作，大规模地制得具有高导电性能和高机械性能的柔软石墨烯纸，以此石墨烯纸为基底制得的石墨烯/聚苯胺复合纸在超级电容器电极材料领域具有良好的应用前景。
碳纳米管（CNTs）作为一种一维碳材料，重量轻，六边形结构连接完美，独有的一维中空的管状结构使其有很大的长径比，作为吸波材料具有质量轻、电性能好、吸波频带广等优点。近些年随着碳纳米管及纳米材料研究的深入其广阔的应用前景也不断地展现出来。碳纳米管可以作为效果良好的吸波和电磁屏蔽材料，而碳纳米管的优秀机械性能使其成为良好的复合材料添加物。将聚苯胺纤维与碳纳米管复合得到的新型复合纸材料具有优异的导电性。然而，聚苯胺在聚合时往往会发生团聚作用，影响其导电性和稳定性。尚没有一种有效地方法解决在制备聚苯胺纤维与碳纳米管复合纸材料时聚苯胺的团聚问题。
发明内容
针对在制备聚苯胺纤维与碳纳米管复合纸材料时聚苯胺的团聚问题的技术缺陷，本发明提出一种高导电复合纸，通过将纳米氧化锌粒子均匀分散在聚苯胺当中，使得聚苯胺生长在碳纳米管的表面，并且将纳米碳管完全包覆在内，作为造纸纤维原材料进行造纸，解决了苯胺聚合时的团聚问题，制备的复合纸具有优异的导电性。
为解决上述问题，本发明采用以下技术方案：一种高导电复合纸，所述高导电复合纸原料中含有一种碳纳米管/聚苯胺/氧化锌三相复合导电材料，所述三相复合导电材料由包括如下原料按重量份制备而成：
碳纳米管粉料 10-15份
纳米氧化锌粉料 10-15份
肉桂酸 5-10份
二甲基硅油 2-8份
聚乙烯蜡 2-6份
EVA 1-5份
聚苯胺 25-30份
N,N-二甲基甲酰胺 25-45份
优选的，所述碳纳米管为单壁碳纳米管、双壁碳纳米管、多壁碳纳米管和表面活化的碳纳米管中的一种或几种的混合，所述碳纳米管的长度范围为10-100纳米，所述纳米氧化锌粉料为缺氧的氧化锌颗粒，所述氧化锌颗粒的粒径为3-20nm。
优选的，一种高导电复合纸的制备方法，包括以下制备步骤：
（1）按重量份称取各组分原料；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在75-100℃下搅拌50-90分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70-90℃，转速为250-500rpm，搅拌50-120分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，超声波振荡2-4h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:10-25，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为70-90℃，转速为270-600rpm，搅拌50-120分钟，得到一种碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将所述复合导电悬浊液与纸纤维浆料混合，经过抄造工艺，制备纸样，在90-110℃下烘干即得。
优选的，所述第（2）步中聚苯胺溶入过程中保持超声振荡20-30分钟，超声功率为3~5kW。
优选的，所述第（3）步中纳米氧化锌分散于聚苯胺中之后，经过老化3-5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降。
优选的，所述浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为6~7:4~3。
优选的，所述复合导电悬浊液与纸纤维浆料的体积比为1:1~3.2，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1 : 0~1: 0.5: 0.1配合，与3倍的水制备的浆料，所述植物纤维为松木纤维、慈竹纤维、桉木纤维、麦草纤维、苇纤维、蔗渣纤维中的一种或几种的混合，所述矿物纤维为石棉纤维和玻璃纤维中的一种或两种的混合，所述分散剂为聚丙烯酰胺、聚氧化乙烯、甘油、聚乙烯醇、聚乙烯吡咯烷酮、纤维素、十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵中的一种或几种的混合，所述粘合剂为聚乙烯醇、改性淀粉、水溶性酚醛树脂、阿拉伯胶、二硫赤藓糖醇中的一种或几种的混合。
现有方案中尚没有一种有效地方法解决在制备聚苯胺纤维与碳纳米管复合纸材料时聚苯胺的团聚问题。鉴于此，本发明提出一种复合纸及其制备方法，利用超声技术，使纳米氧化锌粒子均匀分散在聚苯胺当中，聚苯胺生长在碳纳米管的表面，并且将纳米碳管完全包覆在内，制备出一种碳纳米管/聚苯胺/氧化锌三相复合导电材料，把它应用于纸中就形成一种高导电复合纸，本发明不但解决了苯胺聚合时的团聚问题，还可以使纳米氧化锌粒子均匀的分散在聚苯胺结构当中，有效的提高了聚苯胺的导电性能和稳定性。该方法制备的复合纸具有优异的导电性，易于实现规模化工业生产。
本发明提供一种复合纸及其制备方法，与现有技术相比，其突出的特点和优异的效果在于：
1、本发明提供的一种复合纸及其制备方法，使纳米氧化锌粒子均匀分散在聚苯胺当中，使得聚苯胺生长在碳纳米管的表面,并且将纳米碳管完全包覆在内，制备出一种碳纳米管/聚苯胺/氧化锌三相复合导电材料作为抄纸原料，解决了聚苯胺作为造纸原料在抄纸过程聚合时的团聚问题，提高了复合纸的导电性。
2、本发明提供的一种复合纸及其制备方法，利用超声技术,制备出一种碳纳米管/聚苯胺/氧化锌三相复合导电材料，使纳米氧化锌粒子均匀的分散在聚苯胺结构当中,有效的提高了聚苯胺的导电性能和稳定性，进而制备的复合纸具有优异的导电性。
3、本方案制备工艺简单，获得的产品质量较高，产品性能稳定，应用范围广，推动了碳纳米管复合纸材料的推广应用。
具体实施方式
以下通过具体实施方式对本发明作进一步的详细说明，但不应将此理解为本发明的范围仅限于以下的实例。在不脱离本发明上述方法思想的情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均应包含在本发明的范围内。
实施例1
（1）按重量份称取10份长度为100纳米的单壁碳纳米管粉料，15份粒径为20nm缺氧的氧化锌颗粒粉料，5份肉桂酸， 8份二甲基硅油，2份聚乙烯蜡，5份EVA，25份聚苯胺，30份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡30分钟，超声功率3kW，在100℃下搅拌50分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70℃，转速为500rpm，搅拌50分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化3分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为6:4，超声波振荡4h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1: 25，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为90℃，转速为270rpm，搅拌50分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:1.2的复合导电悬浊液与纸纤维浆料混合，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 0: 0.5: 0.1配合，与3倍的水打制的浆料，所述植物纤维为松木纤维，所述矿物纤维为玻璃纤维，所述分散剂为聚丙烯酰胺，所述粘合剂为聚乙烯醇，经过抄造工艺，制备纸样，在90℃下烘干即得。
对实施例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
实施例2
（1）按重量份称取15份长度为10纳米的多壁碳纳米管和表面活化的碳纳米管的混合碳纳米管粉料， 15份粒径为3nm缺氧的氧化锌颗粒粉料，5份肉桂酸，5份二甲基硅油，5份聚乙烯蜡，1份EVA，29份聚苯胺，25份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡20分钟，超声功率为5kW，在75℃下搅拌90分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为90℃，转速为250rpm，搅拌120分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化3-5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为7:3，超声波振荡2h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:10，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为70℃，转速为600rpm，搅拌120分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:2的所述复合导电悬浊液与纸纤维浆料混合，纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 1: 0.5: 0.1配合，与3倍的水打制浆料，植物纤维为慈竹纤维，矿物纤维为石棉纤维，分散剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化的混合，所述粘合剂为阿拉伯胶，经过抄造工艺，制备纸样，在110℃下烘干即得。
对实施例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
实施例3
（1）按重量份称取12份长度为50纳米的表面活化的碳纳米管粉料，12份粒径为10nm缺氧的氧化锌颗粒粉料，6份肉桂酸，5份二甲基硅油，5份聚乙烯蜡，1份EVA，27份聚苯胺，32份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡20-30分钟，超声功率为3~5kW，在75-100℃下搅拌50-90分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为90℃，转速为280rpm，搅拌100分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化3.5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为6.5:3.5，超声波振荡2.5h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:10，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为85℃，转速为300rpm，搅拌100分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:3的所述复合导电悬浊液与纸纤维浆料混合，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 0.1: 0.5: 0.1配合，与3倍的水打制浆料，所述植物纤维为麦草纤维、苇纤维混合，矿物纤维为石棉纤维，分散剂为聚丙烯酰胺、聚氧化乙烯、甘油中的混合，所述粘合剂为聚乙烯醇、改性淀粉、水溶性酚醛树脂的混合，经过抄造工艺，制备纸样，在100℃下烘干即得。
对实施例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
实施例4
（1）按重量份称取13份长度为80纳米的单壁碳纳米管、双壁碳纳米管混合碳纳米管粉料，12份粒径为15nm缺氧的氧化锌颗粒粉料，5份肉桂酸，2份二甲基硅油，5份聚乙烯蜡，3份EVA，30份聚苯胺，35份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡28分钟，超声功率为5kW，在90℃下搅拌55分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为85℃，转速为450rpm，搅拌80分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化3-5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为7: 3，超声波振荡3h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:15，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为75℃，转速为500rpm，搅拌110分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:2.5的所述复合导电悬浊液与纸纤维浆料混合，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 1: 0.5: 0.1配合，在于3倍的水打制而成的浆料，所述植物纤维为松木纤维，所述矿物纤维为石棉纤维和玻璃纤维中的混合，分散剂为甘油，所述粘合剂为改性淀粉，经过抄造工艺，制备纸样，在95℃下烘干即得。
对实施例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
实施例5
（1）按重量份称取13份长度为40纳米的单壁碳纳米管，13份粒径为15nm缺氧的氧化锌颗粒粉料，10份肉桂酸，2份二甲基硅油， 6份聚乙烯蜡，2份EVA， 30份聚苯胺，30份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡25分钟，超声功率为4.5kW，在95℃下搅拌85分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70-90℃，转速为400rpm，搅拌95分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为6:4，超声波振荡2.5h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:15，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为75℃，转速为300rpm，搅拌90分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:2的所述复合导电悬浊液与纸纤维浆料混合，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 0.5: 0.5: 0.1配合，与3倍的水打制而成的浆料，所述植物纤维为苇纤维，所述矿物纤维为石棉纤维和玻璃纤维中的混合，所述分散剂为聚丙烯酰胺、聚氧化乙烯的混合，所述粘合剂为聚乙烯醇、改性淀粉、二硫赤藓糖醇中的混合，经过抄造工艺，制备纸样，在105℃下烘干即得。
对实施例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
对比例1
（1）按重量份称取13份长度为40纳米的单壁碳纳米管，13份粒径为15nm缺氧的氧化锌颗粒粉料，2份二甲基硅油， 6份聚乙烯蜡，2份EVA， 30份聚苯胺，30份N,N-二甲基甲酰胺；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在溶入过程中保持超声振荡25分钟，超声功率为4.5kW，在95℃下搅拌85分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70-90℃，转速为400rpm，搅拌95分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，纳米氧化锌分散于聚苯胺中之后，经过老化5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降，得到氧化锌聚苯胺溶液；
（4）将碳纳米管与所述氧化锌聚苯胺溶液混合，控制溶液温度为75℃，转速为300rpm，搅拌90分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将体积比为1:2的所述复合导电悬浊液与纸纤维浆料混合，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1: 0.5: 0.5: 0.1配合，与3倍的水打制而成的浆料，所述植物纤维为苇纤维，所述矿物纤维为石棉纤维和玻璃纤维中的混合，所述分散剂为聚丙烯酰胺、聚氧化乙烯的混合，所述粘合剂为聚乙烯醇、改性淀粉、二硫赤藓糖醇中的混合，经过抄造工艺，制备纸样，在105℃下烘干即得。
对比例中制备获得的复合纸进行性能测试后，获得数据如表1所示。
表1
性能指标 密度（g/cm³ 电导率（S/m） 拉伸强度（MPa）
实施例1 0.52 1098 34
实施例2 0.45 1072 33
实施例3 0.47 998 37
实施例4 0.53 975 35
实施例5 0.49 1043 33
对比例1 0.51 458 36

Claims (7)

1.一种高导电复合纸，其特征在于，所述高导电复合纸原料中含有一种碳纳米管/聚苯胺/氧化锌三相复合导电材料，所述三相复合导电材料由包含如下原料按重量份制备而成：
碳纳米管粉料 10-15份
纳米氧化锌粉料 10-15份
肉桂酸 5-10份
二甲基硅油 2-8份
聚乙烯蜡 2-6份
EVA 1-5份
聚苯胺 25-30份
N,N-二甲基甲酰胺 25-45份；
所述高导电复合纸由如下方法制备得到：
（1）按重量份称取各组分原料；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在75-100℃下搅拌50-90分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70-90℃，转速为250-500rpm，搅拌50-120分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，超声波振荡2-4h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:10-25，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为70-90℃，转速为270-600rpm，搅拌50-120分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将所述复合导电悬浊液与纸纤维浆料混合，经过抄造工艺，制备纸样，在90-110℃下烘干即得。
2.根据权利要求1所述的一种高导电复合纸，其特征在于，所述碳纳米管为单壁碳纳米管、双壁碳纳米管、多壁碳纳米管和表面活化的碳纳米管中的一种或几种的混合，所述碳纳米管的长度范围为10-100纳米，所述纳米氧化锌粉料为缺氧的氧化锌颗粒，所述氧化锌颗粒的粒径为3-20nm。
3.一种制备如权利要求1-2任一项所述高导电复合纸的方法，其特征在于，包括以下制备步骤：
（1）按重量份称取各组分原料；
（2）将聚苯胺溶入N,N-二甲基甲酰胺中，在75-100℃下搅拌50-90分钟，得到聚苯胺溶液；
（3）依次将纳米氧化锌粉料、二甲基硅油、聚乙烯蜡、EVA加入所述聚苯胺溶液，控制温度为70-90℃，转速为250-500rpm，搅拌50-120分钟，纳米氧化锌粒子均匀分散在聚苯胺溶液中，得到氧化锌聚苯胺溶液；
（4）将碳纳米管粉料进行表面处理，将碳纳米管加入适量浓硫酸双氧水混合溶液中，超声波振荡2-4h，过滤后用去离子水洗涤至中性，活化碳纳米管与去离子水按质量比1:10-25，配成悬浊液，加入肉桂酸，搅拌，超声波分散1min，得到改性的碳纳米管分散溶液；
（5）将所述改性的碳纳米管分散溶液与所述氧化锌聚苯胺溶液混合，控制溶液温度为70-90℃，转速为270-600rpm，搅拌50-120分钟，得到碳纳米管/聚苯胺/氧化锌三相复合导电材料悬浊液，将所述复合导电悬浊液与纸纤维浆料混合，经过抄造工艺，制备纸样，在90-110℃下烘干即得。
4.根据权利要求3所述的一种高导电复合纸的制备方法，其特征在于，所述第（2）步中聚苯胺溶入过程中保持超声振荡20-30分钟，超声功率为3~5kW。
5.根据权利要求3所述的一种高导电复合纸的制备方法，其特征在于，所述第（3）步中纳米氧化锌分散于聚苯胺中之后，经过老化3-5分钟，使得纳米氧化锌表面包覆二甲基硅油、聚乙烯蜡、EVA材料，防止纳米氧化锌粉末沉降。
6.根据权利要求3所述的一种高导电复合纸的制备方法，其特征在于，所述浓硫酸双氧水混合溶液中浓硫酸与双氧水的体积比为6~7:4~3。
7.根据权利要求3所述的一种高导电复合纸的制备方法，其特征在于，所述复合导电悬浊液与纸纤维浆料的体积比为1:1~3.2，所述纸纤维浆料为植物纤维、矿物纤维、分散剂、粘合剂按质量比例为1 : 0~1: 0.5: 0.1配合，与3倍的水打制的浆料，所述植物纤维为松木纤维、慈竹纤维、桉木纤维、麦草纤维、苇纤维、蔗渣纤维中的一种或几种的混合，所述矿物纤维为石棉纤维和玻璃纤维中的一种或两种的混合，所述分散剂为聚丙烯酰胺、聚氧化乙烯、甘油、聚乙烯醇、聚乙烯吡咯烷酮、纤维素、十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵中的一种或几种的混合，所述粘合剂为聚乙烯醇、改性淀粉、水溶性酚醛树脂、阿拉伯胶、二硫赤藓糖醇中的一种或几种的混合。
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