CN113264770A - 一种抗弯折MXene/碳复合材料散热膜制备方法 - Google Patents

一种抗弯折MXene/碳复合材料散热膜制备方法 Download PDF

Info

Publication number
CN113264770A
CN113264770A CN202110583225.4A CN202110583225A CN113264770A CN 113264770 A CN113264770 A CN 113264770A CN 202110583225 A CN202110583225 A CN 202110583225A CN 113264770 A CN113264770 A CN 113264770A
Authority
CN
China
Prior art keywords
mxene
heat dissipation
film
carbon composite
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110583225.4A
Other languages
English (en)
Other versions
CN113264770B (zh
Inventor
张鑫
路馨语
牛永安
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang University of Chemical Technology
Original Assignee
Shenyang University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang University of Chemical Technology filed Critical Shenyang University of Chemical Technology
Priority to CN202110583225.4A priority Critical patent/CN113264770B/zh
Publication of CN113264770A publication Critical patent/CN113264770A/zh
Application granted granted Critical
Publication of CN113264770B publication Critical patent/CN113264770B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3839—Refractory metal carbides
    • C04B2235/3843—Titanium carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3856—Carbonitrides, e.g. titanium carbonitride, zirconium carbonitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
    • C04B2235/3886—Refractory metal nitrides, e.g. vanadium nitride, tungsten nitride
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

本发明公开了一种抗弯折MXene/碳复合材料散热膜制备方法，涉及一种复合材料散热膜制备方法，首先采用聚酰亚胺（polyimide）作为基体，刻蚀MAX相得到的MXene颗粒作为增强材料，易成碳聚合物作为中间层，经过充分混合、反应、涂膜、固化形成MXene/成碳聚合物/聚酰亚胺复合膜。其次将制备的MXene/成碳聚合物/聚酰亚胺复合膜装入高温碳化炉中，保护气氛下进行高温热解与碳化形成MXene/碳复合材料。最后用水与乙醇反复清洗其表面，获得抗弯折MXene/碳复合材料散热膜。该方法制备的MXene/碳复合材料散热膜不仅具备优异的耐热性以及散热性，且其质轻强度高，具有突出的抗弯折性能，可用于大功率电子设备、LED背底、微电子与传感器件等散热。

Description

一种抗弯折MXene/碳复合材料散热膜制备方法
技术领域
本发明涉及一种散热膜制备方法，特别是涉及一种抗弯折MXene/碳复合材料散热膜制备方法。
背景技术
5G、6G网络高速发展阶段，智能手机、笔记本电脑等智能设备离不开CPU等芯片，芯片与散热器之间存在很多沟壑或空隙，充斥着大量空气，然而空气的热阻值很高，因此通常采用其他介质降低热阻。特别是，智能机及电脑等电子设备终究归向便携式、多功能化的方向发展，在方便生活的同时，由于散热问题，同时也成为威胁人类安全的隐患。因此，芯片散热问题也是电子领域的研究热点。
常用的导热硅胶、硅脂由于其黏着性很强，残留物很难清除；而碳化的聚酰亚胺（polyimide）膜，由于其具有低密度、高散热性、能有效反射电磁波和较高的导热系数等优点，具有广阔的应用前景。现在大部分电子设备的散热膜是石墨膜及复合石墨膜、碳化的聚酰亚胺膜等材料，其中石墨膜制备复杂、密度较大、难以成型，制备出的膜厚度为0.1mm左右，其结构缺陷多、散热性较差；碳化的聚酰亚胺膜的厚度通常只有几微米(μm)，其密度较小、散热较好，但柔韧性差、不易存储运输，在装备使用过程中消耗过大，所以仅使用纯的碳化聚酰亚胺膜的成本造价过高。
MXene材料柔韧度强、密度低，且导热性好。MXene材料一般是由M层和X层组成，M可以是Ti，X可以是C，因此具有很好的稳定性。MXene可以在聚合物中自由运动获得均匀分布，在很大程度上保留了MXene的二维层片状结构特性而不被破坏，为制备具有优异机械柔韧性的MXene复合材料提供了可能性。由于MXene是二维层状结构，原子和原子之间存在较大空隙，所以在与聚合物进行复合时，一些聚合物分子可分布在双层结构之间，形成了良好的导热通路，实现力学与导热性能协同增强。因此，将MXene材料和碳化的聚酰亚胺复合制备散热膜，不仅制备方法简单、可行性强，且成本低，能够较好地弥补单一碳化聚酰亚胺膜的性能不足。
发明内容
本发明的目的在于提供一种抗弯折MXene/碳复合材料散热膜制备方法，该方法将MXene材料分散在DMAc等有机溶剂中，使MXene能够与聚酰亚胺前驱体均匀地混合，方法简单，易于操作；所加入层状MXene材料，有效地弥补纯聚酰亚胺碳化后柔韧性的不足，制备的MXene/碳复合材料具有较高的导热性、柔韧性和综合性能，解决了现有散热膜不抗弯折的问题。
本发明的目的是通过以下技术方案实现的：
一种抗弯折MXene/碳复合材料散热膜制备方法，所述方法包括如下制备步骤：
（1）将易成碳聚合物和MXene颗粒溶于极性溶剂中，超声、搅拌形成均匀、稳定的混合溶液；
（2）将上述混合溶液按比例加入到聚酰亚胺前驱体溶液中，搅拌、共混形成MXene/易成聚合物/聚酰亚胺复合前驱体；
（3）采用涂膜工艺涂覆于平板形成前驱体膜，放入固化炉中，经过热固化形成具有三层结构的MXene/易成聚合物/聚酰亚胺复合膜；
（4）将MXene/易成聚合物/聚酰亚胺复合膜放入碳化炉，在惰性气体保护氛围下进行高温碳化，降温冷却后再用溶剂清洗其表面，制得抗弯折MXene/碳复合材料散热膜。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（1）中易成碳聚合物为碳含量大于50%的聚醚醚酮、聚酰亚胺、环氧树脂、酚醛树脂、双马来酰亚胺、聚芳炔中的任意一个或任意组合。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（1）中MXene颗粒是二维层状结构Ti2C、Ti3C2、Ti2N、Ti3N2、Ti4N3、Ti3(CN)、Zr2C、Zr3C2、Zr2N、Zr3N2、Zr3N3、Hf2C、Hf2C3、Hf2N、Hf3N2、Hf3N3、V2C、V4C3、V2N、V2N2、V2N3、Cr2C、Cr2C2、Cr2N、Mo2C、Mo2C2、Mo2N、Nb2C、Nb4C3、Nb2N、Ta2C、Ta4C3、Ta2N、Sc2C中的任意一个或任意组合，平均厚度为0.1~10nm，平均粒径为10~10000nm，使用前需经过1~50wt%的氢氟酸刻蚀0.5~12h。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（1）中极性溶剂为水、甲醇、乙醇、甲苯、甲酰胺、三氟乙酸、二甲基亚砜、乙腈、N，N-二甲基甲酰胺（DMF）、N，N-二甲基乙酰胺（DMAc）、六甲基磷酰胺、乙酸、异丙醇、吡啶、四甲基乙二胺、丙酮、三乙胺、正丁醇、二氧六环、四氢呋喃、甲酸甲酯、三丁胺、甲乙酮、乙酸乙酯、氯仿、三辛胺、碳酸二甲酯、乙醚、异丙醚、正丁醚、三氯乙烯、二苯醚、二氯甲烷、二氯乙烷、环己烷、N-甲基吡咯烷酮中的一种或以任意比例组合。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（1）中易成碳聚合物为极性溶剂用量的0.01~20wt%，MXene颗粒为极性溶剂用量的0.01~40wt%，搅拌时间为0.1~5小时，形成均匀稳定的混合溶液为胶体溶液。
所述一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（2）中聚酰亚胺前驱体为聚酰亚胺、聚酰胺酸或其衍生物的溶液，浓度为0.1~50wt%，溶剂为上述权利要求4所指的极性溶剂，前驱体的用量为MXene颗粒用量的0.1~500倍，搅拌时间为0.1~5小时。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（3）中涂膜工艺包括旋涂、刮涂、喷涂、蘸涂、滴涂、模具法、半烘干法。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（3）中混合溶液涂覆成膜，在涂覆过程中控制膜的厚度在0.1~1000μm之间；固化过程温度为100~500℃，保温时间为0.1~24小时。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（4）中碳化膜的清洗采用水或乙醇反复清洗1~5次。
所述的一种抗弯折MXene/碳复合材料散热膜制备方法，所述步骤（4）中惰性气体为氮气、氩气、氦气中的任意一种或任意组合；碳化温度为500~2000℃，保温时间为0.1~24小时。
本发明的优点与效果是：
（1）本发明通过加热、再混合的方法将MXene材料分散在DMAc等有机溶剂中，使MXene能够与聚酰亚胺前驱体均匀地混合，方法简单，易于操作；
（2）本发明所加入了层状MXene材料，呈双层结构，同层原子紧密排列，显示出良好的柔韧性，将其与聚酰亚胺复合碳化，可以有效地弥补纯聚酰亚胺碳化后柔韧性的不足。
（3）MXene和聚酰亚胺为主要原料制备的MXene/碳复合材料具有较高的导热性、柔韧性和综合性能，能解决现有散热膜不抗弯折的问题。
附图说明
图1是MXene/碳复合材料的微观形貌图；
图2是MXene/碳复合材料散热效果模拟图；
图3是不同温度下制备的MXene/碳复合材料的XRD图谱。
具体实施方式
下面结合附图所示实施例对本发明进行详细说明。
实施例1
首先，将0.5g洗涤、干燥后的Ti3C2的MXene颗粒加入0.1g的易成碳聚酰亚胺和20mL的N，N-二甲基乙酰胺超声分散，搅拌1小时后形成包覆易成碳聚酰亚胺包覆的Ti3C2胶体溶液。其次，将5g的聚酰胺酸前驱体溶液加入胶体溶液，搅拌溶液1小时使其混合、摇匀，制得MXene/易成碳聚酰亚胺/聚酰胺酸混合前驱体溶液；然后，将上述混合前驱体溶液喷涂于基板上，放入固化炉中在100℃，200℃分别处理2小时，再升温到300℃固化3小时，制备的MXene/易成碳聚酰亚胺/聚酰亚胺复合膜。最后，将上述复合膜放入高温碳化炉中，在氮气保护下升温到1500℃，保温2h，待冷却后取出，用水与乙醇分别清洗3次，得到的抗弯折MXene/碳复合材料散热膜。经测试，散热膜的导热系数为217W/mK，面密度为84.76g/m2，失重率为40.64%。
实施例2
首先，将0.6g洗涤、干燥后的Ti2N的MXene颗粒加入0.06g的易成碳双马来酰亚胺和15mL的N，N-二甲基乙酰胺超声分散，搅拌2小时后形成包覆易成碳聚酰亚胺包覆的Ti2N胶体溶液。其次，将10g的聚酰亚胺前驱体溶液加入胶体溶液，搅拌溶液1.5小时使其混合、摇匀，制得MXene/易成碳双马来酰亚胺/聚酰亚胺混合前驱体溶液；然后，将上述混合前驱体溶液刮涂于基板上，放入固化炉在100℃，200℃，300℃分别处理2小时，再升温到350℃固化1小时，制备的产物MXene/易成碳双马来酰亚胺/聚酰亚胺复合膜。最后，将上述复合膜放入高温碳化炉中，在氩气保护下升温到1400℃，保温3h，待冷却后取出，得到的抗弯折MXene/碳复合材料散热膜。经测试，散热膜的导热系数为201W/mK，面密度为85.56g/m2，失重率为40.33%。
以上实施例并不是全部实施方式的列举。在本发明基础上的步骤替换、变换、改进等实现制备抗弯折MXene/碳复合材料散热膜的技术方案，也在本发明的权利要求范围之内。

Claims (10)

1.一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述方法包括如下制备步骤：
（1）将易成碳聚合物和MXene颗粒溶于极性溶剂中，超声、搅拌形成均匀、稳定的混合溶液；
（2）将上述混合溶液按比例加入到聚酰亚胺前驱体溶液中，搅拌、共混形成MXene/易成聚合物/聚酰亚胺复合前驱体；
（3）采用涂膜工艺涂覆于平板形成前驱体膜，放入固化炉中，经过热固化形成具有三层结构的MXene/易成聚合物/聚酰亚胺复合膜；
（4）将MXene/易成聚合物/聚酰亚胺复合膜放入碳化炉，在惰性气体保护氛围下进行高温碳化，降温冷却后再用溶剂清洗其表面，制得抗弯折MXene/碳复合材料散热膜。
2.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（1）中易成碳聚合物为碳含量大于50%的聚醚醚酮、聚酰亚胺、环氧树脂、酚醛树脂、双马来酰亚胺、聚芳炔中的任意一个或任意组合。
3.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（1）中MXene颗粒是二维层状结构Ti2C、Ti3C2、Ti2N、Ti3N2、Ti4N3、Ti3(CN)、Zr2C、Zr3C2、Zr2N、Zr3N2、Zr3N3、Hf2C、Hf2C3、Hf2N、Hf3N2、Hf3N3、V2C、V4C3、V2N、V2N2、V2N3、Cr2C、Cr2C2、Cr2N、Mo2C、Mo2C2、Mo2N、Nb2C、Nb4C3、Nb2N、Ta2C、Ta4C3、Ta2N、Sc2C中的任意一个或任意组合，平均厚度为0.1~10nm，平均粒径为10~10000nm，使用前需经过1~50wt%的氢氟酸刻蚀0.5~12h。
4.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（1）中极性溶剂为水、甲醇、乙醇、甲苯、甲酰胺、三氟乙酸、二甲基亚砜、乙腈、N，N-二甲基甲酰胺（DMF）、N，N-二甲基乙酰胺（DMAc）、六甲基磷酰胺、乙酸、异丙醇、吡啶、四甲基乙二胺、丙酮、三乙胺、正丁醇、二氧六环、四氢呋喃、甲酸甲酯、三丁胺、甲乙酮、乙酸乙酯、氯仿、三辛胺、碳酸二甲酯、乙醚、异丙醚、正丁醚、三氯乙烯、二苯醚、二氯甲烷、二氯乙烷、环己烷、N-甲基吡咯烷酮中的一种或以任意比例组合。
5.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（1）中易成碳聚合物为极性溶剂用量的0.01~20wt%，MXene颗粒为极性溶剂用量的0.01~40wt%，搅拌时间为0.1~5小时，形成均匀稳定的混合溶液为胶体溶液。
6.根据权利要求1所述一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（2）中聚酰亚胺前驱体为聚酰亚胺、聚酰胺酸或其衍生物的溶液，浓度为0.1~50wt%，溶剂为上述权利要求4所指的极性溶剂，前驱体的用量为MXene颗粒用量的0.1~500倍，搅拌时间为0.1~5小时。
7.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（3）中涂膜工艺包括旋涂、刮涂、喷涂、蘸涂、滴涂、模具法、半烘干法。
8.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（3）中混合溶液涂覆成膜，在涂覆过程中控制膜的厚度在0.1~1000μm之间；固化过程温度为100~500℃，保温时间为0.1~24小时。
9.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（4）中碳化膜的清洗采用水或乙醇反复清洗1~5次。
10.根据权利要求1所述的一种抗弯折MXene/碳复合材料散热膜制备方法，其特征在于，所述步骤（4）中惰性气体为氮气、氩气、氦气中的任意一种或任意组合；碳化温度为500~2000℃，保温时间为0.1~24小时。
CN202110583225.4A 2021-05-27 2021-05-27 一种抗弯折MXene/碳复合材料散热膜制备方法 Active CN113264770B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110583225.4A CN113264770B (zh) 2021-05-27 2021-05-27 一种抗弯折MXene/碳复合材料散热膜制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110583225.4A CN113264770B (zh) 2021-05-27 2021-05-27 一种抗弯折MXene/碳复合材料散热膜制备方法

Publications (2)

Publication Number Publication Date
CN113264770A true CN113264770A (zh) 2021-08-17
CN113264770B CN113264770B (zh) 2022-11-11

Family

ID=77233150

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110583225.4A Active CN113264770B (zh) 2021-05-27 2021-05-27 一种抗弯折MXene/碳复合材料散热膜制备方法

Country Status (1)

Country Link
CN (1) CN113264770B (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060124693A1 (en) * 2004-12-15 2006-06-15 Meloni Paul A Thermally conductive polyimide film composites having high mechanical elongation useful as a heat conducting portion of an electronic device
CN102560453A (zh) * 2012-03-08 2012-07-11 哈尔滨工业大学 利用石墨烯增强聚酰亚胺树脂碳化制备碳化膜的方法
CN110330646A (zh) * 2019-06-21 2019-10-15 广东工业大学 一种柔性聚酰亚胺基复合介电薄膜材料及其制备方法和应用
CN110354697A (zh) * 2019-06-24 2019-10-22 大连理工大学盘锦产业技术研究院 一种基于MXene材料的混合基质膜及其制备方法
CN111471300A (zh) * 2020-06-01 2020-07-31 中国科学院合肥物质科学研究院 一种导热聚酰亚胺绝缘膜及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060124693A1 (en) * 2004-12-15 2006-06-15 Meloni Paul A Thermally conductive polyimide film composites having high mechanical elongation useful as a heat conducting portion of an electronic device
CN102560453A (zh) * 2012-03-08 2012-07-11 哈尔滨工业大学 利用石墨烯增强聚酰亚胺树脂碳化制备碳化膜的方法
CN110330646A (zh) * 2019-06-21 2019-10-15 广东工业大学 一种柔性聚酰亚胺基复合介电薄膜材料及其制备方法和应用
CN110354697A (zh) * 2019-06-24 2019-10-22 大连理工大学盘锦产业技术研究院 一种基于MXene材料的混合基质膜及其制备方法
CN111471300A (zh) * 2020-06-01 2020-07-31 中国科学院合肥物质科学研究院 一种导热聚酰亚胺绝缘膜及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨以娜等: "MXenes在柔性力敏传感器中的应用研究进展", 《无机材料学报》 *

Also Published As

Publication number Publication date
CN113264770B (zh) 2022-11-11

Similar Documents

Publication Publication Date Title
Niu et al. Highly transparent and self‐healable solar thermal anti‐/deicing surfaces: when ultrathin MXene multilayers marry a solid slippery self‐cleaning coating
Zhu et al. Fabrication of high‐performance silver mesh for transparent glass heaters via electric‐field‐driven microscale 3D printing and UV‐assisted microtransfer
Li et al. 3D printed high performance silver mesh for transparent glass heaters through liquid sacrificial substrate electric‐field‐driven jet
CN105405492B (zh) 具备高热稳定性的柔性透明导电薄膜的制备方法及其产品
TWI625226B (zh) 可撓性透明聚醯亞胺積層板及其製造方法
Tiwari et al. Healable and flexible transparent heaters
US20230183138A1 (en) Integrated polymer-derived ceramic thin-film sensor produced by layser pyrolysis and additive manufacturing and fabrication method thereof
JP2016530622A (ja) 電子的構成要素とパターン化ナノワイヤ透明伝導体との接合
Zhang et al. Electrical, mechanical, and electromagnetic shielding properties of silver nanowire‐based transparent conductive films
CN106318250A (zh) 导热双面胶带的制备工艺
KR101859005B1 (ko) 복합 방열 필름
CN102775865A (zh) 散热涂料及其制备方法和应用
CN107338426A (zh) 一种在聚酰亚胺薄膜表面生长高粘结性银金属图案的方法
Wang et al. Flexible substrate based on sandwich-structure hydrocarbon resin/aligned boron nitride composites with high thermal conductivity and low dielectric loss
CN113264770B (zh) 一种抗弯折MXene/碳复合材料散热膜制备方法
WO2014181930A1 (ko) 이방성 열 전기전도 액정 조성물 및 이를 이용한 방열 및 전자파 차폐 매트릭스의 제조방법
CN106297964A (zh) 一种复合透明导电薄膜及其制备方法
Dong et al. Bioinspired High‐Adhesion Metallic Networks as Flexible Transparent Conductors
Zhang et al. Adhesion and thermal stability enhancement of IZO films by adding a primer layer on polycarbonate substrate
CN102390146B (zh) 散热物表面设置传热层以及散热层的制作方法以及散热层状结构
Dwivedi et al. Robustification of ITO nanolayer by surface‐functionalization of transparent biopolyimide substrates
CN107722272B (zh) 聚酰亚胺薄膜的制备方法
KR101508202B1 (ko) 수직 배열된 그래핀을 포함하는 방열 코팅층의 형성방법
KR101924857B1 (ko) 열전도성 입자
Qi et al. Direct Ion Exchange Self‐Metallization: A Novel and Efficient Route for the Preparation of Double‐Surface‐Silvered Polyimide Films

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant