CN208158919U - Graphene heating film and graphene suitable for power battery pack heat membrane module - Google Patents

Graphene heating film and graphene suitable for power battery pack heat membrane module Download PDF

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Publication number
CN208158919U
CN208158919U CN201721925502.0U CN201721925502U CN208158919U CN 208158919 U CN208158919 U CN 208158919U CN 201721925502 U CN201721925502 U CN 201721925502U CN 208158919 U CN208158919 U CN 208158919U
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graphene
heating
membrane module
silica gel
film
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刘斌
王田军
黄小华
杜野
吴菲
罗平
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Shenzhen Hoverbird Electronic Technology Co Ltd
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Shenzhen Hoverbird Electronic Technology Co Ltd
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/10Energy storage using batteries

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Abstract

This application involves technical field of graphene and heating element technical field, specifically disclose a kind of graphene heating film and a kind of graphene heating membrane module.The graphene heating film includes organic macromolecule-based film and the heating line at least one surface of the organic polymer basement membrane, and the heating line is by the way that graphene conductive slurry to be applied at least one described surface and be solidified to form.Graphene heating membrane module with heat conductive silica gel, graphene thermally conductive sheet, organic polymer insulating film and temperature sensor by combining the graphene heating film being made.High conductivity, high-termal conductivity, high mechanical strength and the high-flexibility of graphene is utilized in the graphene heating membrane module of the utility model, have many advantages, such as that heating voltage is low, heating speed is fast, electrothermal efficiency is high, heating surface uniformly, without rubescent red-hot phenomenon, can be windability good, soft, frivolous, conformal good.Suitable for providing heat source for power battery pack, influence of the low temperature charge and discharge to battery performance is solved.

Description

Graphene heating film and graphene suitable for power battery pack heat membrane module
Technical field
This application involves technical field of graphene and heating element technical field, and in particular to a kind of graphene heating film Membrane module is heated with a kind of graphene, is especially adapted for use in the graphene heating film and graphene heating film group of power battery pack Part.
Background technique
The evident characteristic that electric automobile power battery charges at low temperature at present is that voltage rises rapidly, and is charged at low temperature It will cause positive lithium and fall off that fast, cathode lithium insertion speed is slow, cause lithium metal accumulate generation dendrite at the electrode surface, easily wear out Battery diaphragm makes battery short circuit, constitutes security risk.Therefore, under cryogenic, power battery is preferably heated so that battery In room temperature state (20-30 DEG C) charge and discharge.
A kind of heating method is heated using PTC fever tablet.PTC fever tablet is semiconductive ceramic, the disadvantage is that weight Amount is big, heating efficiency is low, volume size is big, without flexibility, hard crisp, inflexibility winding.Another way is using heating film It is heated.The plane heater element that heating film is made of electrically insulating material with the heating resistor material encapsulated in it.Hair Hotting mask needs to can be only achieved heating effect in very high voltage, radiation heat loss is very big, and heating circuit does not have since resistance is big Good flexibility is easy open circuit in the process of bending, bad in terms of heat-resisting, wearability, moisture-proof and safety.
Graphene is a kind of flat film being made of carbon atom, and the connection between internal carbon atom is very flexible.Graphite Its electron mobility is more than 15000cm to alkene at normal temperature2/ (Vs), thermal coefficient is up to 5300W/ (mK), and resistivity Only about 10-6Ω cm, it is lower than copper or silver, it is the current the smallest material of world resistivity.Graphene is under the voltage lower than 12V It is obtained with good heating effect.
Summary of the invention
To overcome problem of the prior art, the object of the present invention is to provide a kind of graphene heating films and a kind of graphene to add Hotting mask component is particularly useful for the graphene heating membrane module of electric automobile power battery packet.
Therefore, in one aspect, the present invention provides a kind of graphene heating film, which includes organic high score Subbase film and the heating line at least one surface of the organic polymer basement membrane, the heating line is by by graphene Electrocondution slurry is applied at least one surface and is solidified to form.
Specifically, which includes the graphene 1-10 parts by weight of epoxy-functional, epoxy resin 4-15 Parts by weight, epoxy-modified siloxanes 2-6 parts by weight, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1-0.8 Parts by weight.
Preferably, which also includes through silane coupler modified conductive black 5-20 parts by weight, resists Wire drawing agent 0.2-1 parts by weight and 0.05-0.2 parts of antioxidant.
Specifically, which is PET film.
Specifically, which completed by way of spraying or silk-screen printing, preferably passes through silk-screen printing Mode is completed.Spraying and screen printing technique in electrocondution slurry field application be it is known in the art that see, for example, with Page 16 of Publication about Document:Li Jiang, Electric radiant Heating Film and silk-screen printing,《Silk-screen printing》, 01 phase in 1996.
Specifically, which completed by 100-150 DEG C of infrared heating 5-12 minutes.
On the other hand, the present invention provides a kind of graphene heating membrane module, and it includes root which, which heats membrane module, According to the graphene heating film of first aspect present invention, the first heat conductive silica gel, the second heat conductive silica gel, the first graphene thermally conductive sheet, Two graphene thermally conductive sheets, the first organic polymer insulating film and the second organic polymer insulating film, wherein first heat conductive silica gel Positioned at the top of the graphene heating film, which is located at the top of first heat conductive silica gel, this first has Machine polymer insulating film is located at the top of the first graphene thermally conductive sheet, which is located at the graphene heating film Lower section, the second graphene thermally conductive sheet are located at the lower section of second heat conductive silica gel, which is located at should The lower section of second graphene thermally conductive sheet.
Preferably, graphene heating membrane module further includes temperature sensor, and wherein the temperature sensor is located at first and leads Between hot silica gel and the first graphene thermally conductive sheet, or between the second heat conductive silica gel and the second graphene thermally conductive sheet.
Preferably, which is commercially available sheet type temperature sensor, such as ultra-thin temperature sensors of high precision.
Preferably, first organic polymer insulating film and the second organic polymer insulating film are commercially available PE insulating film.
Preferably, the first graphene thermally conductive sheet and the second graphene thermally conductive sheet are commercially available graphene thermally conductive sheet.
Preferably, first heat conductive silica gel and the second heat conductive silica gel are commercially available heat conductive silica gel.
Preferably, first organic polymer insulating film and the second organic polymer insulating film are commercially available PE insulating film.
Beneficial effects of the present invention
The present invention, as host conductive agent, makes full use of the high conductivity of graphene, especially with this Shen using graphene The ask someone graphene conductive slurry of exploitation produces graphene heating film, then by with heat conductive silica gel, graphene thermally conductive sheet and PE Insulating film combination is made graphene heating membrane module, gained subassembly product after tested, operating voltage<12V, resistance are 3~5 Ω, Cold insulation resistance>300M Ω, hot insulation resistance>3 DEG C of 200M Ω, temperature uniformity <, in addition maximum operation (service) temperature is 60 DEG C, have that heating voltage is low, heating speed is fast, electrothermal efficiency is high, heating surface uniformly, without rubescent red-hot phenomenon, energy-saving safe Advantage.
Meanwhile the present invention makes full use of the high-termal conductivity of graphene.Graphene thermal conductivity is up to 4000-6600W/mK, Compared with graphite and traditional heat-dissipating material, quick conductive characteristic that graphene has.Graphene heating membrane module of the invention is adopted Use graphene thermally conductive sheet that quick conductive may be implemented as the transmitting medium of heat.
Moreover, graphene has high mechanical strength and high-flexibility, electric silica gel and PE insulating film softness are frivolous, manufactured Graphene heats membrane module can be windability good, soft, frivolous, long service life.It can be according to being heated battery pack Arbitrary shape bending, it is ensured that be in close contact with battery pack, guarantee the transmitting of maximum thermal energy, significantly save battery pack space and The weight for reducing battery pack, improves the volume energy density and gravimetric energy density of battery pack.
By configuring ultra-thin high-accuracy temperature sensor, real time monitoring is heated in the temperature and power battery pack of membrane module Portion's temperature can carry out humanized perforation, guarantee the stability of temperature, the peace of battery pack by the intelligent temperature controller on automobile The convenience of full property and manipulation.Suitable for batteries of electric automobile packet, heat source is provided for battery pack, solves low temperature charge and discharge to battery The influence of performance.
Detailed description of the invention
Fig. 1 is the schematic diagram of the graphene heating film of an embodiment according to the present invention.Appended drawing reference in figure is such as Under:1- graphene heating film;2- heat conductive silica gel;3- graphene thermally conductive sheet;4-PE insulating film.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing, invention is further described in detail.
Graphene heating film of the invention includes organic macromolecule-based film and positioned at least the one of the organic polymer basement membrane Heating line on a surface, the heating line is by the way that graphene conductive slurry to be applied at least one surface and solidify And it is formed.
(I) component of the graphene conductive slurry
The graphene conductive slurry includes following components:The graphene 1-10 parts by weight of epoxy-functional, epoxy resin 4- 15 parts by weight, epoxy-modified siloxanes 2-6 parts by weight, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1- 0.8 parts by weight.
Preferably, which is the epoxy resin with pi bond structure.It is highly preferred that the epoxy resin is with benzene The epoxy resin of ring structure.It is more preferred still that the epoxy resin be bisphenol A type epoxy resin or bisphenol f type epoxy resin, especially It is electron level bisphenol A type epoxy resin or bisphenol f type epoxy resin.Most preferably, which is bisphenol F type epoxy Resin, because bisphenol f type epoxy resin has good high-temperature stability, to multiple materials such as metal, plastics, rubber, ceramics With good adhesive property.
The graphene of the epoxy-functional is made by the way that graphene powder is carried out surface functionalization with the epoxy resin, Wherein the weight ratio of the epoxy resin and the graphene powder is 1:4-3:1.Preferably, with Bisphenol F type epoxy resin by graphite Alkene powder carries out surface functionalization.
The epoxy-modified siloxanes is, wherein asphalt mixtures modified by epoxy resin obtained by being modified siloxanes with the epoxy resin The weight ratio of rouge and the siloxanes is 1:3-2:1, wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyl dihydro two At least one of siloxanes, tetramethyl divinyl disiloxane or t etram-ethyltetravinylcyclotetrasiloxane.Preferably, it uses Silicone powder is carried out surface functionalization by bisphenol f type epoxy resin.
Preferably, which also includes 5-20 parts by weight through silane coupler modified conductive black. The silane coupler modified conductive black is, wherein silane obtained by being modified conductive black with silane coupling agent Coupling agent accounts for the 0.8%-2.5% of the weight of the conductive black.Preferably, which is γ-(2,3- the third oxygen of epoxy) Propyl trimethoxy silicane (KH560).
Preferably, the graphene conductive slurry also include 0.2-1 parts by weight the agent of tension silk and 0.05-0.2 parts of antioxygen Agent.The tension silk agent can prevent the graphene conductive slurry from occurring wire drawing phenomenon in use, and the antioxidant Help to prevent the oxidation of graphene conductive slurry.
Graphene used in the graphene conductive slurry is graphene powder well known in the art, preferably high conductivity Graphene powder is less than in graphene powder preparation process using element dopings graphene, the numbers of plies of graphene powder such as N, B 5 layers.The available commercial quotient of this graphene is, for example, Xi Wang new material Science and Technology Co., Ltd. of Shenzhen, the hexa-atomic element in Changzhou Limited liability company, Changzhou two dimension carbon Science and Technology Co., Ltd. etc..
Conductive black used in the graphene conductive slurry is conductive black well known in the art, such as Japanese lion princes and dukes Take charge of the serial superconducting carbon black (Ketjenblack EC-300J and EC-600JD) of Ketjenblack (Ketjen black), the beauty of (LION) The VXC series of conductive carbon black of Cabot Co., Ltd of state (CABOT) wins the production of wound Degussa (Evonik Degussa) company PRINTEX XE2-B, PRINTEX L6, HIBLAXK 40B2 etc..
The epoxy active diluent is ethylene glycol diglycidylether, butanediol diglycidyl ether, 1,6- cyclohexandiol Diglycidyl ether, tetrahydrophthalic acid 2-glycidyl ester, hexahydrophthalic acid 2-glycidyl ester, 1,2- hexamethylene two At least one of alcohol diglycidyl ether or resorcinolformaldehyde resin.
The latent curing agent is group of the lanthanides boron trifluoride acetic acid complex compound La (BF3·C4H7O4)n、 Sm(BF3·C4H7O4) n、Dy(BF3·C4H7O4)n、Er(BF3·C4H7O4) n or Yb (BF3·C4H7O4At least one of) n, wherein (BF3· C4H7O4) n expression boron trifluoride acetic acid anion, n expression complexing coefficient.
The tension silk agent is at least one of nano-titanium dioxide, nano zine oxide, Nano carbon white.It is highly preferred that The tension silk agent is A380 white carbon black.
The antioxidant is bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyl) sebacates, bis- (2,2,6,6- Tetramethyl -4- piperidyl) sebacate, 4- [(the pungent sulfenyl -1,3,5- triazine -2- base of 4,6- bis-) amino] -2,6- di-t-butyl At least one of phenol, dimethylsuccinic acid esters -4- hydroxyl -2,2,6,6- tetramethyl -4- piperidine alcohols.
(II) preparation method of the graphene conductive slurry
The preparation method of the graphene conductive slurry includes the following steps:
The epoxy-functional of graphene powder:Graphene powder is subjected to epoxy-functional with epoxy resin, wherein the ring The weight ratio of oxygen resin and the graphene powder is 1:4-3:1;
Siloxanes it is epoxy-modified:Siloxanes is modified with epoxy resin, wherein the epoxy resin and the siloxanes Weight ratio be 1:3-2:1;
Mixing:By surface functionalized graphene powder 1-10 parts by weight, through epoxy-modified siloxanes 2-6 Parts by weight, epoxy resin 4-15 parts by weight, epoxy active diluent 2-6 parts by weight and latent curing agent 0.1-0.8 weight Part carries out low speed dispersion stirring, high speed dispersion stirring, vacuum defoamation, and the graphene conductive slurry is made.
Preferably, which is the epoxy resin with pi bond structure.It is highly preferred that the epoxy resin is with benzene The epoxy resin of ring structure.It is more preferred still that the epoxy resin be bisphenol A type epoxy resin or bisphenol f type epoxy resin, especially It is electron level bisphenol A type epoxy resin or bisphenol f type epoxy resin.Most preferably, which is bisphenol F type epoxy Resin, because bisphenol f type epoxy resin has good high-temperature stability, to multiple materials such as metal, plastics, rubber, ceramics With good adhesive property.
Preferably, the epoxy-functional step of the graphene powder includes by the graphene powder and epoxy resin anhydrous In solvent, in 20-120 DEG C of temperature, power 500W-4800W, frequency is ultrasonic wave, the 300rpm- of 30KHz-120KHz Concussion processing 1-8 hours under the rotation of 3500rpm, then vacuum filter is dry under conditions of being lower than 50 DEG C, removes solvent, system The graphene of epoxy-functional is obtained, wherein the solvent is dehydrated alcohol, isopropanol, butanol, ethyl acetate, butyl acetate, acetic acid One of pentyl ester, isoamyl acetate, isoamyl acetate, n-methyl-2-pyrrolidone (NMP) or several mixtures.
Preferably, the epoxy-modified step of the siloxanes includes by toluene, epoxy resin, catalyst platinum tetrachloride in logical nitrogen 15min is stirred under conditions of gas, wherein the weight ratio of toluene and the epoxy resin is 1.2:1-3.0:1, catalyst four Platinum chloride accounts for the 0.008%-0.05% of weight epoxy, and gained mixture is then warming up to 70 DEG C in a nitrogen atmosphere, It is added dropwise the 1 of toluene and siloxanes:1-5:1 mixed liquor 1h, the reaction was continued 6h, vacuum distillation remove toluene solvant, obtain epoxy and change The siloxanes of property, wherein the siloxanes is tetramethyl tetrahydro cyclotetrasiloxane, tetramethyldihydrogendisiloxane, tetramethyl divinyl At least one of base disiloxane or t etram-ethyltetravinylcyclotetrasiloxane.
It preferably, further include being changed conductive black in acidic aqueous solution with silane coupling agent before the mixing step Property, wherein the silane coupling agent accounts for the 0.8%-2.5% of the weight of the conductive black;The mixing step includes being additionally added 5-20 weight The modified conductive black for measuring part carries out mixing.Preferably, which is γ-(2,3- the third oxygen of epoxy) propyl three Methoxy silane (KH560).
Preferably, which includes being additionally added the agent of tension silk and 0.05-0.2 parts anti-oxidant of 0.2-1 parts by weight Agent carries out mixing.
Preferably, which carries out in contactless planet stirring vacuum defoamation all-in-one machine, the contactless row The vacuum degree of planetary stirring vacuum deaeration all-in-one machine is -0.095MPa;When low speed dispersion stirring, revolution revolving speed is 100- 500rpm, the ratio between revolution and rotational velocity are 1:5-2:1, time 10min-120min;When high speed dispersion stirs, revolution revolving speed is 800-5000rpm, the ratio between revolution and rotational velocity are 1:2-3:1, time 15min-80min.
The graphene, the conductive black, the epoxy active diluent, the latent curing agent, the tension silk agent and this is anti- Oxidant is as described in the first aspect of the invention.
Moreover, it is noted that carrying out ring to the graphene for the first aspect of the present invention and second aspect The functionalized epoxy resin of oxygen carries out epoxy-modified epoxy resin to the siloxanes and as the master of the graphene conductive slurry The epoxy resin of one of body component can be identical or can not be identical.Such as the graphene carries out the asphalt mixtures modified by epoxy resin of epoxy-functional Rouge, the epoxy that one of epoxy-modified epoxy resin and the host component as the graphene conductive slurry are carried out to the siloxanes Resin can be each independently bisphenol A type epoxy resin or bisphenol f type epoxy resin.
(III) preparating example of the graphene conductive slurry
Preparating example 1
In this preparating example, to graphene carry out epoxy-functional epoxy resin, siloxanes is carried out it is epoxy-modified The epoxy resin of one of epoxy resin and host component as graphene conductive slurry is all made of bisphenol A type epoxy resin.It should Bisphenol A type epoxy resin is purchased from Shenzhen Jia Dida Chemical Co., Ltd., model NPEL-128E.
By the 2g graphene powder (graphene of the high conductivity of Xi Wang new material Science and Technology Co., Ltd. of Shenzhen preparation Powder), 3.5g bisphenol A type epoxy resin and 200g dehydrated alcohol be added in high speed rotation cavity testing machine.The high speed is revolved Turn cavity testing machine and is configured with supersonic generator and heating constant-temperature equipment.By mixture at 20-120 DEG C, 1600rpm high speed is revolved Turn and 2000W, frequency 80KHz ultrasonic wave under shake 1-8h hour, then vacuum filter is done under conditions of lower than 50 DEG C It is dry, solvent is removed, the graphene powder of surface functionalization is made.
200g toluene, 80g bisphenol A type epoxy resin, 0.02g catalyst platinum tetrachloride are added in glass container, Under the mixing speed of 200rpm, 15min is stirred under conditions of logical nitrogen.Then mixture is heated up in a nitrogen atmosphere To 70 DEG C.The mixed liquor 1h of 80g toluene and 20g tetramethyl tetrahydro cyclotetrasiloxane is added dropwise using dropping funel.After being added dropwise, The reaction was continued 6h, vacuum distillation remove toluene solvant, obtain epoxy-modified siloxanes.
Siloxanes epoxy-modified obtained by graphene powder surface-functionalized obtained by 10g, 4g, 10g is bis- Phenol A type epoxy resin, 4g ethylene glycol diglycidylether, 0.5g La (BF3·C4H7O4) n, 0.5gA380 white carbon black and 0.1g Bis- (1- octyloxy -2,2,6,6- tetramethyl -4- piperidyls) sebacates are added in glass container, in the stirring speed of 120rpm It is stirred until homogeneous under degree.Then the contactless planet stirring vacuum defoamation one that vacuum degree is -0.095MPa is fed the mixture into In body machine, low speed dispersion stirring is first carried out, revolution revolving speed is 100-500rpm, and the ratio between revolution and rotational velocity are 1:5-2:1, Mixing time is 40min, and when then carrying out high speed dispersion stirring, revolution revolving speed is 800~5000rpm, revolution and rotational velocity The ratio between be 1:2-3:1, mixing time 30min, then vacuum removal bubble, is made the graphene conductive slurry of this preparating example Material.
Preparating example 2
In this preparating example, to graphene carry out epoxy-functional epoxy resin, siloxanes is carried out it is epoxy-modified The epoxy resin of one of epoxy resin and host component as graphene conductive slurry is all made of bisphenol f type epoxy resin generation For the bisphenol A type epoxy resin in preparating example 1, remaining is identical as preparating example 1.The bisphenol f type epoxy resin is purchased from deep Jia Dida Chemical Co., Ltd. of ditch between fields city, model NPEF-170.
Preparating example 3
In this preparating example, the epoxy resin of epoxy-functional is carried out to graphene and siloxanes is carried out epoxy-modified Epoxy resin is all made of the bisphenol A type epoxy resin in preparating example 1, one of host component as graphene conductive slurry For epoxy resin using the bisphenol f type epoxy resin in preparating example 2, remaining is identical as preparating example 1.
Preparating example 4
In this preparating example, the epoxy resin of epoxy-functional is carried out to graphene and siloxanes is carried out epoxy-modified Epoxy resin is all made of the bisphenol f type epoxy resin in preparating example 2, one of host component as graphene conductive slurry For epoxy resin using the bisphenol A type epoxy resin in preparating example 1, remaining is identical as preparating example 1.
Preparating example 5-8
Preparating example 5-8 is corresponding with preparating example 1-4 respectively, but carries out what surface was modified to conductive black increasing Step, and the modified conductive black in obtained surface is prepared into graphene conductive slurry together with remaining component.
Specifically, it using the conductive carbon black Ketjenblack EC-300J of Japanese lion princes and dukes department (LION), and uses It is modified that KH560 silane coupling agent carries out surface to the conductive black.By 100g conductive carbon black Ketjenblack EC-300J and 1.2g KH560 silane coupling agent concentration be 0.5% dilute sulfuric acid aqueous solution in, 40~80 DEG C at a temperature of reaction 0.6~ 2 hours, obtain the modified conductive black in surface.
For preparating example 5, by each component described in the resulting surface 20g modified conductive black and preparating example 1 into Row is mixed, and wherein the graphene of epoxy-functional is changed to 1g by 10g, and presses described in preparating example 1 in contactless row Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in star stirring vacuum deaeration all-in-one machine, obtain graphene conductive Slurry.
For preparating example 6, by each component described in the resulting surface 15g modified conductive black and preparating example 2 into Row is mixed, and wherein the graphene of epoxy-functional is changed to 2.5g by 10g, and presses described in preparating example 1 contactless Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in planet stirring vacuum defoamation all-in-one machine, are obtained graphene and are led Plasma-based material.
For preparating example 7, by each component described in the resulting surface 10g modified conductive black and preparating example 3 into Row is mixed, and wherein the graphene of epoxy-functional is changed to 5g by 10g, and presses described in preparating example 1 in contactless row Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in star stirring vacuum deaeration all-in-one machine, obtain graphene conductive Slurry.
For preparating example 8, each component described in the resulting surface 5g modified conductive black and preparating example 4 is carried out It is mixed, wherein the graphene of epoxy-functional is changed to 7.5g by 10g, and presses described in preparating example 1 in contactless row Low speed dispersion stirring, high speed dispersion stirring and vacuum defoamation are carried out in star stirring vacuum deaeration all-in-one machine, obtain graphene conductive Slurry.
Illustrate that graphene heating film and graphene of the invention heat membrane module with embodiment below.These embodiments are to show Example property, it must not believe that and be construed as limiting the invention.The scope of the present invention is limited only by the claims.
Embodiment 1
This example demonstrates that an embodiment of graphene heating film of the invention.
By any preparating example in " preparating example of (III) the graphene conductive slurry " above, stone is prepared Black alkene electrocondution slurry.
PET polymeric membrane (being purchased from Dongguan City Sheng He Electron Material Co., Ltd, thickness 0.075-0.2mm) is chosen, is selected Solar battery screen printer (is purchased from Shenzhen all-pass wire mark mechanical & electronic equipment corporation, Ltd), and first designs the heating of graphene heating film Line map is fabricated to screen printing forme.
PET polymeric membrane is placed on the print station of solar battery screen printer, screen printing forme is fixed on screen frame, set In the top of PET polymeric membrane, at a distance of 2-30 millimeters.Suitable graphene conductive slurry is added on silk screen, is scratched with scraper Slurry is filled in it uniformly among mesh, and slurry is expressed to PET high score by screen mesh in the process of moving by scraper On one surface of sub- film, heater circuit is printed out.It can depend on the needs and equally print out heater circuit on the other surface.
The PET polymeric membrane for having printed heater circuit is placed in infrared furnace, is carried out at 100-150 DEG C red Outside line solidifies 5-12 minutes, and the graphene heating film of the present embodiment is made.
Embodiment 2
This example demonstrates that an embodiment of graphene heating membrane module of the invention.
Vacuum filling heat conductive silica gel (is purchased from Shenzhen Jia Feng Electron Material Co., Ltd), implements heat conductive silica gel package Graphene heating film made from example 1 makes graphene heating film upper and lower surface respectively have one layer of electric silica gel, and every layer with a thickness of 0.08- 0.4mm.By ultra-thin temperature sensors of high precision (Wuxi Zhong Hui automotive electronics Co., Ltd) be placed in Upper conductive silica gel or under On the surface of layer electric silica gel.Ultra-thin temperature sensors of high precision with a thickness of 0.2mm, temperature-measuring range is -40 DEG C to 100 DEG C, Zero-power resistance is R25=10K Ω ± 0.5%, and material constant is B25/85=3370K ± 0.5%, reaction speed about 1s.
The graphene fever black upper and lower surface achieved above wrapped up with heat conductive silica gel is successively used into (the purchase of graphene thermally conductive sheet (Foshan is purchased from from the supply of Xi Wang new material Science and Technology Co., Ltd. of Shenzhen, thickness 0.05mm-0.5mm) and PE insulating film Nan Mu new material Co., Ltd of city, thickness 0.05-0.3mm) it clips, it is then placed within ultrasonic wave thermosol pressing curing and (is purchased from Dongguan City Long Ke automation equipment Science and Technology Ltd.;Frequency 20KHZ, power 2000W, 100-150 DEG C of temperature, weld interval 0.5-10s), the graphene that the present embodiment is made heats membrane module.
Obtained graphene heating membrane module is according to GB/T 7287-2008《Infrared radiation heater test method》With GB/T4208-2008《Waterproofing grade test method》It is tested for the property.Test item, test method and test result is as follows:
As seen from the above table, using grapheme material as host conductive agent, prepared graphene heats membrane module Operating voltage<12V, resistance are 3-5 Ω, cold insulation resistance>300M Ω, hot insulation resistance>200M Ω, temperature uniformity 3 DEG C of <, in addition maximum operation (service) temperature is 60 DEG C, has that heating voltage is low, heating speed is fast, planar heating, energy-saving safe it is excellent Point.
Use above specific example is expounded the present invention, is merely used to help understand the present invention, not to The limitation present invention.The design of those skilled in the art according to the present invention can also be made and several simply push away It drills, deform or replaces.These are deduced, deformation or alternative are also fallen into scope of the presently claimed invention.

Claims (10)

1. a kind of graphene heating film, which is characterized in that the graphene heating film include organic macromolecule-based film and be located at institute The heating line at least one surface of organic polymer basement membrane is stated, the heating line is by applying graphene conductive slurry It is added at least one described surface and is solidified to form.
2. graphene heating film according to claim 1, which is characterized in that the graphene conductive slurry includes epoxy official Graphene 1-10 parts by weight, epoxy resin 4-15 parts by weight, the epoxy-modified siloxanes 2-6 parts by weight, epoxy-reactive of energyization Diluent 2-6 parts by weight and latent curing agent 0.1-0.8 parts by weight.
3. graphene heating film according to claim 2, which is characterized in that the graphene conductive slurry also includes through silicon The coupling agent modified conductive black 5-20 parts by weight of alkane, tension silk agent 0.2-1 parts by weight and 0.05-0.2 parts of antioxidant.
4. graphene heating film according to any one of claim 1-3, which is characterized in that the organic polymer basement membrane For PET film, described apply is completed by way of silk-screen printing, and the solidification is by 100-150 DEG C of infrared heating It 5-12 minutes completes.
5. a kind of graphene heats membrane module, which is characterized in that the graphene heating membrane module includes according to claim 1-4 Any one of described in graphene heating film, the first heat conductive silica gel, the second heat conductive silica gel, the first graphene thermally conductive sheet, the second stone Black alkene thermally conductive sheet, the first organic polymer insulating film and the second organic polymer insulating film, wherein first heat conductive silica gel position In the top of the graphene heating film, the first graphene thermally conductive sheet is located at the top of first heat conductive silica gel, described First organic polymer insulating film is located at the top of the first graphene thermally conductive sheet, and second heat conductive silica gel is located at the stone The lower section of black alkene heating film, the second graphene thermally conductive sheet are located at the lower section of second heat conductive silica gel, and described second is organic Polymer insulating film is located at the lower section of the second graphene thermally conductive sheet.
6. graphene according to claim 5 heats membrane module, which is characterized in that the graphene heating membrane module also wraps Include temperature sensor, wherein the temperature sensor between first heat conductive silica gel and the first graphene thermally conductive sheet or Between second heat conductive silica gel and the second graphene thermally conductive sheet.
7. graphene according to claim 6 heats membrane module, which is characterized in that the temperature sensor is commercially available thin slice Type temperature sensor.
8. graphene according to claim 6 or 7 heats membrane module, which is characterized in that the first graphene thermally conductive sheet It is commercially available graphene thermally conductive sheet with the second graphene thermally conductive sheet.
9. graphene according to claim 6 or 7 heats membrane module, which is characterized in that first heat conductive silica gel and the Two heat conductive silica gels are commercially available heat conductive silica gel.
10. graphene according to claim 6 or 7 heats membrane module, which is characterized in that first organic polymer is exhausted Velum and the second organic polymer insulating film are commercially available PE insulating film.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112757724A (en) * 2020-12-29 2021-05-07 宁波世一科技有限责任公司 Flexible metal-based graphene electrothermal material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112757724A (en) * 2020-12-29 2021-05-07 宁波世一科技有限责任公司 Flexible metal-based graphene electrothermal material and preparation method thereof
CN112757724B (en) * 2020-12-29 2022-05-20 杭州宜联研仿科技有限公司 Preparation method of flexible metal-based graphene electrothermal material

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