CN106317440A - 一种石墨烯复合导热膜的制备方法 - Google Patents

一种石墨烯复合导热膜的制备方法 Download PDF

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CN106317440A
CN106317440A CN201610690289.3A CN201610690289A CN106317440A CN 106317440 A CN106317440 A CN 106317440A CN 201610690289 A CN201610690289 A CN 201610690289A CN 106317440 A CN106317440 A CN 106317440A
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    • C08J2381/06—Polysulfones; Polyethersulfones

Abstract

本发明公开了一种石墨烯复合导热膜的制备方法，该方法可无污染、能批量化生产的制备石墨烯，利用氧化石墨烯分散液作为喷涂液，避免直接使用石墨烯喷涂，既节约成本，又可以保证原料的质量，同时氧化石墨烯具有含氧基团，具有亲水性，与衬底结合力比石墨烯更强，使膜层更有韧性，再通过还原得到石墨烯，从而提高导热膜的产量和质量。

Description

一种石墨烯复合导热膜的制备方法
技术领域
本发明涉及电子产品散热领域，具体涉及一种石墨烯复合导热膜的制备方法。
背景技术
对于电子产品而言，其各个部件有效的散热来获得较低的工作温度对其使用寿命和运行速度会产生极其重要的影响。随着科技的不断发展和进步，特别是计算机芯片多核化已经成为主流，且运行速度不断加快，功率也随之增长，有效的散热对其运行速度起着举足轻重的作用。目前，市场上的散热主流产品为石墨类导热膜，然而，其散热性能远远满足不了电子信息产品散热器件的散热需求，成为了大多电子产品的散热瓶颈。
石墨烯（Graphene）是一种由碳原子以sp2杂化轨道组成六角型呈蜂巢晶格（honeycomb crystal lattice）排列构成的单层平面薄膜，只有一个碳原子厚度的二维材料。石墨烯目前是世上最薄却也是最坚硬的纳米材料，它几乎是完全透明的，只吸收2.3%的光；导热系数高达5300W/m·K，高于碳纳米管和金刚石，常温下其电子迁移率超过15000cm2/(V·s)，又比纳米碳管或硅晶体高，而电阻率只约10-6 Ω·cm，比铜或银更低，为世上电阻率最小的材料。石墨烯具有如此优异的物理化学性能，已逐渐用于透明导电薄膜，纳米电子器件（晶体管，晶体管电路互联内存半导体），导电墨水，太阳能电池、锂电池、超级电容器、传感器和生物医药等领域。
目前石墨烯的制备方法存在成本高且对环境污染严重等问题，因而需要寻求一种低成本、无污染的方法以实现石墨烯的批量化生产。
发明内容
本发明提供一种石墨烯复合导热膜的制备方法，该方法可无污染、能批量化生产的制备石墨烯，利用氧化石墨烯分散液作为喷涂液，避免直接使用石墨烯喷涂，既节约成本，又可以保证原料的质量，同时氧化石墨烯具有含氧基团，具有亲水性，与衬底结合力比石墨烯更强，使膜层更有韧性，再通过还原得到石墨烯，从而提高导热膜的产量和质量。
为了实现上述目的，本发明提供了一种石墨烯复合导热膜的制备方法，该方法包括如下步骤：
（1）制备氧化石墨烯溶液
将250g天然石墨和由4.5L浓硫酸和0.5L浓磷酸组成的5L混酸混合于反应釜内并用电控磁力搅拌器搅拌均匀，在低于20℃的情况下缓慢加入500g高锰酸钾；之后，密封反应釜并升温至85-90℃反应2-3小时，将产物从反应釜下端取出，稀释成40L溶液，加入0.6L双氧水得亮黄色氧化石墨溶液；然后，用酸和水交替离心洗涤，至溶液pH=5-6，去除杂质离子；最后，超声分散氧化石墨，配置出一定浓度的氧化石墨烯溶液；
（2）在柔性衬底上刷涂粘结剂
柔性衬底为聚合物薄膜的柔性有机材料，选自PET(聚对苯二甲酸乙二醇酯)、PEN(聚对萘二甲酸乙二醇酯)、PC(聚碳酸酯)、PVC(聚氯乙烯)、PS(聚苯乙烯)、PMMA(聚甲基丙烯酸甲酯)、PBT(聚对苯二甲酸丁二醇酯)、PES(聚对苯二乙基砜)；
（3）制备氧化石墨烯薄膜
采用热喷涂法将氧化石墨烯水溶液喷涂在预先刷涂粘结剂的柔性衬底上，喷涂的高度为离衬底40-60cm、温度为100-120℃；
（4）还原得到石墨烯导热膜。
优选的，在步骤（4）中，具体的还原方法为在零度低温下加入还原剂，在120-150℃的柔性衬底上喷涂，然后在真空或者保护气氛中、300-400℃温度下进行热处理，对氧化石墨烯薄膜进一步除氧，得到石墨烯薄膜，所述还原剂为尿素和/或抗坏血酸。
本发明的优点在于，可无污染、能批量化生产的制备石墨烯，利用氧化石墨烯分散液作为喷涂液，避免直接使用石墨烯喷涂，既节约成本，又可以保证原料的质量，同时氧化石墨烯具有含氧基团，具有亲水性，与衬底结合力比石墨烯更强，使膜层更有韧性，再通过还原得到石墨烯，从而提高导热膜的产量和质量。
具体实施方式
实施例一
将250g天然石墨和由4.5L浓硫酸和0.5L浓磷酸组成的5L混酸混合于反应釜内并用电控磁力搅拌器搅拌均匀，在低于20℃的情况下缓慢加入500g高锰酸钾；之后，密封反应釜并升温至85℃反应2小时，将产物从反应釜下端取出，稀释成40L溶液，加入0.6L双氧水得亮黄色氧化石墨溶液；然后，用酸和水交替离心洗涤，至溶液pH=5-6，去除杂质离子；最后，超声分散氧化石墨，配置出一定浓度的氧化石墨烯溶液。
柔性衬底为聚合物薄膜的柔性有机材料，选自PET(聚对苯二甲酸乙二醇酯)、PEN(聚对萘二甲酸乙二醇酯)、PC(聚碳酸酯)、PVC(聚氯乙烯)、PS(聚苯乙烯)、PMMA(聚甲基丙烯酸甲酯)、PBT(聚对苯二甲酸丁二醇酯)、PES(聚对苯二乙基砜)。
采用热喷涂法将氧化石墨烯水溶液喷涂在预先刷涂粘结剂的柔性衬底上，喷涂的高度为离衬底40cm、温度为100℃；具体的还原方法为在零度低温下加入还原剂，在120℃的柔性衬底上喷涂，然后在真空或者保护气氛中、300℃温度下进行热处理，对氧化石墨烯薄膜进一步除氧，得到石墨烯薄膜，所述还原剂为尿素。
实施例二
将250g天然石墨和由4.5L浓硫酸和0.5L浓磷酸组成的5L混酸混合于反应釜内并用电控磁力搅拌器搅拌均匀，在低于20℃的情况下缓慢加入500g高锰酸钾；之后，密封反应釜并升温至90℃反应3小时，将产物从反应釜下端取出，稀释成40L溶液，加入0.6L双氧水得亮黄色氧化石墨溶液；然后，用酸和水交替离心洗涤，至溶液pH=5-6，去除杂质离子；最后，超声分散氧化石墨，配置出一定浓度的氧化石墨烯溶液。
柔性衬底为聚合物薄膜的柔性有机材料，选自PET(聚对苯二甲酸乙二醇酯)、PEN(聚对萘二甲酸乙二醇酯)、PC(聚碳酸酯)、PVC(聚氯乙烯)、PS(聚苯乙烯)、PMMA(聚甲基丙烯酸甲酯)、PBT(聚对苯二甲酸丁二醇酯)、PES(聚对苯二乙基砜)。
采用热喷涂法将氧化石墨烯水溶液喷涂在预先刷涂粘结剂的柔性衬底上，喷涂的高度为离衬底60cm、温度为120℃；具体的还原方法为在零度低温下加入还原剂，在150℃的柔性衬底上喷涂，然后在真空或者保护气氛中、400℃温度下进行热处理，对氧化石墨烯薄膜进一步除氧，得到石墨烯薄膜，所述还原剂为抗坏血酸。

Claims (2)

1.一种石墨烯复合导热膜的制备方法，该方法包括如下步骤：
（1）制备氧化石墨烯溶液
将250g天然石墨和由4.5L浓硫酸和0.5L浓磷酸组成的5L混酸混合于反应釜内并用电控磁力搅拌器搅拌均匀，在低于20℃的情况下缓慢加入500g高锰酸钾；之后，密封反应釜并升温至85-90℃反应2-3小时，将产物从反应釜下端取出，稀释成40L溶液，加入0.6L双氧水得亮黄色氧化石墨溶液；然后，用酸和水交替离心洗涤，至溶液pH=5-6，去除杂质离子；最后，超声分散氧化石墨，配置出一定浓度的氧化石墨烯溶液；
（2）在柔性衬底上刷涂粘结剂
柔性衬底为聚合物薄膜的柔性有机材料，选自PET(聚对苯二甲酸乙二醇酯)、PEN(聚对萘二甲酸乙二醇酯)、PC(聚碳酸酯)、PVC(聚氯乙烯)、PS(聚苯乙烯)、PMMA(聚甲基丙烯酸甲酯)、PBT(聚对苯二甲酸丁二醇酯)、PES(聚对苯二乙基砜)；
（3）制备氧化石墨烯薄膜
采用热喷涂法将氧化石墨烯水溶液喷涂在预先刷涂粘结剂的柔性衬底上，喷涂的高度为离衬底40-60cm、温度为100-120℃；
（4）还原得到石墨烯导热膜。
2.如权利要求1所述的方法，在步骤（4）中，具体的还原方法为在零度低温下加入还原剂，在120-150℃的柔性衬底上喷涂，然后在真空或者保护气氛中、300-400℃温度下进行热处理，对氧化石墨烯薄膜进一步除氧，得到石墨烯薄膜，所述还原剂为尿素和/或抗坏血酸。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325648A (zh) * 2017-06-17 2017-11-07 常州市玉宇化工有限公司 一种石墨烯导热膜的制备方法
CN107599538A (zh) * 2017-08-30 2018-01-19 华南理工大学 一种高性能导热线及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130133373A (ko) * 2012-05-29 2013-12-09 한국과학기술원 자기조립 단분자막과 큰 플레이크 그래핀 산화물의 이온 결합을 이용해 투명하면서도 전기적 특성을 향상시킨 그래핀 필름의 제조 방법
CN103449423A (zh) * 2013-08-27 2013-12-18 常州第六元素材料科技股份有限公司 一种石墨烯导热膜及其制备方法
CN104085143A (zh) * 2014-05-29 2014-10-08 深圳市铭晶科技有限公司 石墨烯复合导热膜的制备方法和产品
CN104150471A (zh) * 2014-07-31 2014-11-19 山东玉皇新能源科技有限公司 一种还原氧化石墨烯的方法
CN104354447A (zh) * 2014-11-19 2015-02-18 江苏悦达新材料科技有限公司 一种新型石墨烯复合导热膜的制备方法
CN105637977A (zh) * 2013-11-22 2016-06-01 东洋德来路博株式会社 碳放热组合物及碳放热体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130133373A (ko) * 2012-05-29 2013-12-09 한국과학기술원 자기조립 단분자막과 큰 플레이크 그래핀 산화물의 이온 결합을 이용해 투명하면서도 전기적 특성을 향상시킨 그래핀 필름의 제조 방법
CN103449423A (zh) * 2013-08-27 2013-12-18 常州第六元素材料科技股份有限公司 一种石墨烯导热膜及其制备方法
CN105637977A (zh) * 2013-11-22 2016-06-01 东洋德来路博株式会社 碳放热组合物及碳放热体
CN104085143A (zh) * 2014-05-29 2014-10-08 深圳市铭晶科技有限公司 石墨烯复合导热膜的制备方法和产品
CN104150471A (zh) * 2014-07-31 2014-11-19 山东玉皇新能源科技有限公司 一种还原氧化石墨烯的方法
CN104354447A (zh) * 2014-11-19 2015-02-18 江苏悦达新材料科技有限公司 一种新型石墨烯复合导热膜的制备方法

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* Cited by examiner, † Cited by third party
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CN107325648A (zh) * 2017-06-17 2017-11-07 常州市玉宇化工有限公司 一种石墨烯导热膜的制备方法
CN107599538A (zh) * 2017-08-30 2018-01-19 华南理工大学 一种高性能导热线及其制备方法
CN107599538B (zh) * 2017-08-30 2019-05-14 华南理工大学 一种高性能导热线及其制备方法

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