CN106187264A - A kind of preparation method with electric heating and heat sinking function thin film - Google Patents

A kind of preparation method with electric heating and heat sinking function thin film Download PDF

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Publication number
CN106187264A
CN106187264A CN201610580547.2A CN201610580547A CN106187264A CN 106187264 A CN106187264 A CN 106187264A CN 201610580547 A CN201610580547 A CN 201610580547A CN 106187264 A CN106187264 A CN 106187264A
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carbon fiber
graphene oxide
thin film
electric heating
solution
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李香粉
陶则超
王宏宝
佟亚伟
刘占军
郭全贵
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83Carbon fibres in a carbon matrix
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/52Shaped 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped 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
    • C04B35/52Shaped 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
    • C04B35/522Graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607Thermal properties, e.g. thermal expansion coefficient

Abstract

A kind of preparation method with electric heating and heat sinking function thin film is graphene oxide solution ultrasonic disperse, obtains graphene oxide solution carbon solution, and carbon fiber substrate is dried after impregnating in poly-vinyl alcohol solution, obtains containing polyvinyl alcohol carbon fiber substrate;To be combined with graphene oxide solution carbon solution containing polyvinyl alcohol carbon fiber substrate, obtain carbon fiber/graphene oxide composite membrane;The carbon fiber obtained/graphene oxide composite membrane is carried out high-temperature hot reduction in inertia or reducing atmosphere, obtains electric heating and heat sinking function thin film.The present invention has low cost, good cycling stability, the advantage that can be mass-produced.

Description

A kind of preparation method with electric heating and heat sinking function thin film
Technical field
The invention belongs to a kind of preparation method being provided simultaneously with electric heating and heat sinking function thin film.
Background technology
In recent years, owing to Environmental degree of concern strengthens, Development of Electric Vehicles is rapid, as electric powered motor source The service behaviour of lithium ion battery and life-span temperature influence very big, when operating ambient temperature is too high, work long hours meeting Internal temperature of battery too high generation temperature protection, electric discharge is caused to stop;When operating ambient temperature is too low, lithium ion activity can drop Low, cause capacity to reduce, even completely lose discharge capability.Prior art improves low temperature ring generally by heating plate etc. Border, and improve hot environment by radiating modes such as fans, such as patent CN 204793107 U, heat radiation is by fan, heating Being to use heating plate, both are implemented in combination with controlling the purpose of temperature, and which can play the purpose of battery thermal management, but by Complicated in its structure, efficiency is low, in-convenience in use;If heating and heat radiation can be united two into one, power source body not only can be reduced Long-pending, and the efficiency of battery can be improved.
Carbon fiber is a kind of fibrous material through high temperature cabonization, and its carbon content is higher than 85%.Carbon fiber has high-strength, low The excellent performance such as close, corrosion-resistant, high temperature resistant, has important using value, by carbon in many fields such as aviation, electronics, machineries Fiber hybrid arrangement forms the matrixes such as carbon fiber paper, and carbon fiber can form conductive network, thus possesses electrically heated function.
Graphene is the hardest the thinnest material known to current world, has the heat-conductivity conducting performance of excellence, heat conduction Coefficient is up to 5300W/ (m K), becomes a nova in heat sink material field.Graphene sheet layer overlap joint forms graphene film can To form heat conduction network, heat conductivity can be the most hundreds of, more excellent than conventional graphite material.The preparation method master of Graphene There are following three kinds: mechanical stripping method, chemical vapour deposition technique, chemistry redox method.Chemistry redox method prepares graphite Alkene low cost, it is possible to achieve scale, is the most the more commonly used method preparing Graphene in a large number.But the stone of preparation at present Ink its electric conductivity of alkene film is the most bad, hardly results in perfect graphene film Rotating fields, graphite mainly due to various preparation methoies The transmission of the defective effect lamella electronics on alkene, and then affect its electric conductivity.
Summary of the invention
It is an object of the invention to provide a kind of radiating efficiency high, conduct electricity very well has electric heating and heat sinking function thin film Preparation method.
The present invention is to possess the carbon fiber product of electrical heating performance as matrix, impregnates in PVAC polyvinylalcohol, regulation and control The micro structure of matrix, is combined with graphene oxide and obtains carbon fiber/graphene oxide (CF/GO) composite membrane, then by its high temperature Thermal reduction, obtains having electric heating and heat sinking function thin film.
Electric heating of the present invention and heat sinking function method for manufacturing thin film, it specifically includes following processing step:
(1) graphene oxide solution ultrasonic disperse, obtains graphene oxide solution carbon solution so that it is lamella separates, thus Form the monolithic layer redox graphene of excellent thermal conductivity;
(2) carbon fiber substrate is dried after impregnating in polyvinyl alcohol (PVA) solution, obtains containing polyvinyl alcohol carbon fiber-based Body, the micro structure of Effective Regulation carbon fiber substrate, thus regulate and control the load capacity of graphene oxide;
(3) step (2) is passed through leaching containing polyvinyl alcohol carbon fiber substrate with step (1) graphene oxide solution carbon solution The modes such as stain, pressure assistant depositing, coating are combined, and obtain carbon fiber/graphene oxide (CF/GO) composite membrane;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane step (3) obtained is in inertia or reducing atmosphere Carry out high-temperature hot reduction, obtain electric heating and heat sinking function thin film.
Graphene oxide as above be mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, chemical oxidation also The one of former method or its mixture;
The concentration of graphene oxide as above is 1-15mg/ml, and ultrasonic time is 20-120min, and ultrasonic power is 100-500W;
The carbon fiber substrate as mentioned above with electric heating function is asphalt base carbon fiber, polyacrylonitrile-based carbon fibre, phenolic aldehyde Paper prepared by the mixture of one or more in base carbon fibre, viscose-based carbon fiber, vapor phase growth base carbon fibre or cloth, carbon is fine Dimension hplc is 10-50g/m2
The temperature of high-temperature hot reduction is 600-1500 DEG C as mentioned above, and heat treatment time is 0.5-6 hour, inertia, reduction Property atmosphere is argon, nitrogen, helium or hydrogen.
Present invention have an advantage that
The invention provides a kind of preparation method with electric heating and heat sinking function thin film, abundant raw material source, preparation Membrane material low cost, intensity is high, and pliability is good, it is easy to industrialized production and use.
The present invention is provided simultaneously with the function of electrical heating and heat radiation, may be used for the heat management aspect of battery, is coated on battery Surface even can be placed in the electrolyte of battery (owing to carbon fiber and Graphene are Carbon Materials, performance temperature and resistance to height Warm, corrosion-resistant, service life length), when ambient temperature is relatively low, electrified regulation improve battery operating temperature, in ambient temperature Time higher, the heat of battery ambient as good heat sink material, can be shifted rapidly, make battery in applicable temperature high efficiency Run.
Low-temperature heat and high temperature are effectively dispelled the heat and are combined by the present invention, the mode phase being combined with heating plate and radiator fan Ratio, has saving volume, alleviates the advantages such as quality and efficiency are high, preparation is simple.
Accompanying drawing explanation
Fig. 1 is the SEM picture of carbon fiber substrate;
Fig. 2 is the SEM picture of electric heating and heat sinking function thin film;
When Fig. 3 is 10cm × 10cm electric heating and heat sinking function thin film electrified regulation, temperature changes over curve.
Detailed description of the invention
Embodiment 1
(1) the 15mg/ml graphene oxide solution that prepared by chemical vapour deposition technique, supersound process under the conditions of 100W 30min, obtains graphene oxide solution carbon solution;
(2) carbon fiber-containing 10g/m2Asphalt base carbon fiber cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained under an argon atmosphere 600 DEG C carry out High-temperature hot reduction 0.5h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 50W/ (m K), and surface resistance is 8.62Ω/cm2
Embodiment 2
(1) supersound process 40min under the conditions of 10mg/ml graphene oxide solution 200W that prepared by epitaxial growth method, obtains Graphene oxide solution carbon solution;
(2)30g/m2Viscose-based carbon fiber cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained under helium atmosphere 800 DEG C carry out High-temperature hot reduction 1h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 80W/ (m K), and surface resistance is 7.51Ω/cm2
Embodiment 3
(1) supersound process 20min under the conditions of 5mg/ml graphene oxide solution 100W that prepared by mechanical stripping method, obtains oxygen Functionalized graphene solution carbon solution;
(2)20g/m2Phenolic aldehyde base carbon fibre cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained in a nitrogen atmosphere 600 DEG C carry out High-temperature hot reduction 3h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 40W/ (m K), and surface resistance is 7.85Ω/cm2
Embodiment 4
(1) supersound process 30min under the conditions of 10mg/ml graphene oxide solution 300W that prepared by chemistry redox method, Obtain graphene oxide solution carbon solution;
(2)40g/m2Gas-phase growth of carbon fibre cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained in a nitrogen atmosphere 1000 DEG C enter Row high-temperature hot reduction 3h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 100W/ (m K), and surface resistance is 6.96Ω/cm2
Embodiment 5
(1) supersound process 30min under the conditions of 1mg/ml graphene oxide solution 100W that prepared by chemistry redox method, To graphene oxide solution carbon solution;
(2)50g/m2Polyacrylonitrile-based carbon fibre cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained in a hydrogen atmosphere 1000 DEG C enter Row high-temperature hot reduction 3h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 120W/ (m K), and surface resistance is 6.88Ω/cm2
Embodiment 6
(1) supersound process 120min under the conditions of 8mg/ml graphene oxide solution 500W that prepared by chemistry redox method, Obtain graphene oxide solution carbon solution;
(2)30g/m2Polyacrylonitrile-based carbon fibre cloth impregnate in polyvinyl alcohol (PVA) solution after dry;
(3) the graphene oxide solution carbon solution in step (1) is coated in step (2) containing polyvinyl alcohol carbon fiber-based Carbon fiber/graphene oxide (CF/GO) composite membrane is obtained after drying on body;
(4) carbon fiber/graphene oxide (CF/GO) composite membrane that step (3) is obtained under an argon atmosphere 1500 DEG C enter Row high-temperature hot reduction 6h obtains having electric heating and heat sinking function thin film.Testing its heat conductivity is 210W/ (m K), and surface resistance is 6.83Ω/cm2
Sample ID Heat conductivity Surface resistance
Carbon fiber substrate 1W/(m·K) 10.86Ω/cm2
Embodiment 1 50W/(m·K) 8.62Ω/cm2
Embodiment 2 80W/(m·K) 7.51Ω/cm2
Embodiment 3 40W/(m·K) 7.85Ω/cm2
Embodiment 4 100W/(m·K) 6.96Ω/cm2
Embodiment 5 120W/(m·K) 6.88Ω/cm2
Embodiment 6 210W/(m·K) 6.83Ω/cm2
Carbon fiber substrate can realize electrified regulation function, but tests its heat conductivity, about 1W/ (m K), face Resistance is 10.86 Ω/cm2, after being combined with Graphene, its thermal diffusion coefficient can improve tens of even hundreds times, can meet As the requirement of heat sink material, the change of its surface resistance is little, still has electric heating function, has widened range of application.
Although the present invention has carried out a certain degree of description, without departing from the scope of, can carry out each The suitably change of individual condition is it can be understood as the invention is not restricted to embodiments described above, and is attributed to the scope of claim, Including the equivalent of described factor, all in this patent scope.

Claims (6)

1. a preparation method with electric heating and heat sinking function thin film, it is characterised in that comprise the steps:
(1) graphene oxide solution ultrasonic disperse, obtains graphene oxide solution carbon solution so that it is lamella separates, thus is formed The monolithic layer redox graphene of excellent thermal conductivity;
(2) carbon fiber substrate is dried after impregnating in poly-vinyl alcohol solution, obtains containing polyvinyl alcohol carbon fiber substrate;
(3) by step (2) containing polyvinyl alcohol carbon fiber substrate and step (1) graphene oxide solution carbon solution by dipping, Pressure assistant depositing or coating method are combined, and obtain carbon fiber/graphene oxide composite membrane;
(4) carbon fiber/graphene oxide composite membrane that step (3) obtains is carried out high-temperature hot also in inertia or reducing atmosphere Former, obtain electric heating and heat sinking function thin film.
A kind of preparation method with electric heating and heat sinking function thin film, it is characterised in that described Graphene oxide is mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, the one of chemistry redox method or its mixing Thing.
A kind of preparation method with electric heating and heat sinking function thin film, it is characterised in that described The concentration of graphene oxide is 1-15mg/ml, and ultrasonic time is 20-120min, and ultrasonic power is 100-500W.
A kind of preparation method with electric heating and heat sinking function thin film, it is characterised in that described carbon Fibrous matrix is asphalt base carbon fiber, polyacrylonitrile-based carbon fibre, phenolic aldehyde base carbon fibre, viscose-based carbon fiber, vapor phase growth base Paper prepared by the mixture of one or more in carbon fiber or cloth, carbon fiber content is 10-50g/m2
A kind of preparation method with electric heating and heat sinking function thin film, it is characterised in that described height The temperature of warm reduction is 600-1500 DEG C, and heat treatment time is 0.5-6 hour.
A kind of preparation method with electric heating and heat sinking function thin film, it is characterised in that inertia, also Originality atmosphere is argon, nitrogen, helium or hydrogen.
CN201610580547.2A 2016-07-21 2016-07-21 A kind of preparation method with electric heating and heat sinking function thin film Pending CN106187264A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107141007A (en) * 2017-05-26 2017-09-08 中国科学院山西煤炭化学研究所 A kind of composite heat conduction film based on graphene and preparation method thereof
CN108823680A (en) * 2018-04-28 2018-11-16 江苏月源纤维科技有限公司 A kind of core-skin type graphene adulterates the preparation method of conductive fiber and yarn
CN110282974A (en) * 2019-06-28 2019-09-27 华南理工大学 Oriented alignment magnetic carbon fiber graphene composite film and its preparation method and application
CN111690160A (en) * 2020-06-08 2020-09-22 安徽福斯特渔具有限公司 Novel high-performance composite material presoaking compounding process
CN112646300A (en) * 2020-12-22 2021-04-13 蜂巢能源科技有限公司 Battery cell buffer material, preparation method and application thereof
CN114773647A (en) * 2022-06-01 2022-07-22 中国科学院过程工程研究所 Carbon fiber prepreg and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482996A (en) * 2013-10-14 2014-01-01 中国科学院山西煤炭化学研究所 Method for preparing carbon fibre and graphene composite paper
CN103801686A (en) * 2013-12-31 2014-05-21 深圳市国创新能源研究院 Graphene nanocomposite and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103482996A (en) * 2013-10-14 2014-01-01 中国科学院山西煤炭化学研究所 Method for preparing carbon fibre and graphene composite paper
CN103801686A (en) * 2013-12-31 2014-05-21 深圳市国创新能源研究院 Graphene nanocomposite and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107141007A (en) * 2017-05-26 2017-09-08 中国科学院山西煤炭化学研究所 A kind of composite heat conduction film based on graphene and preparation method thereof
CN108823680A (en) * 2018-04-28 2018-11-16 江苏月源纤维科技有限公司 A kind of core-skin type graphene adulterates the preparation method of conductive fiber and yarn
CN110282974A (en) * 2019-06-28 2019-09-27 华南理工大学 Oriented alignment magnetic carbon fiber graphene composite film and its preparation method and application
CN111690160A (en) * 2020-06-08 2020-09-22 安徽福斯特渔具有限公司 Novel high-performance composite material presoaking compounding process
CN112646300A (en) * 2020-12-22 2021-04-13 蜂巢能源科技有限公司 Battery cell buffer material, preparation method and application thereof
CN112646300B (en) * 2020-12-22 2023-01-03 蜂巢能源科技有限公司 Battery cell buffer material, preparation method and application thereof
CN114773647A (en) * 2022-06-01 2022-07-22 中国科学院过程工程研究所 Carbon fiber prepreg and preparation method and application thereof
CN114773647B (en) * 2022-06-01 2023-03-03 中国科学院过程工程研究所 Carbon fiber prepreg and preparation method and application thereof

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Application publication date: 20161207