CN105914429A - Flexible heat conductive film based on functional group graphene reduction and preparation method of same - Google Patents
Flexible heat conductive film based on functional group graphene reduction and preparation method of same Download PDFInfo
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- CN105914429A CN105914429A CN201610251132.0A CN201610251132A CN105914429A CN 105914429 A CN105914429 A CN 105914429A CN 201610251132 A CN201610251132 A CN 201610251132A CN 105914429 A CN105914429 A CN 105914429A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a flexible heat conductive film based on functional group graphene reduction and a preparation method of the same. The flexible heat conductive film includes, by weight, 2-10% of graphene micro pieces and 90-98% of a microporous filtering film. The graphene micro pieces can be graphene oxide or nitrogen-doped graphene micro pieces and are 5-80 nm in thickness and are 1-5 [mu]m in size. Through a repeated vacuum-filtering filling method, the graphene micro pieces are embedded into pores in the microporous filtering film. The method is simple and has advantages on large-area preparation of the heat conductive film. The heat conductive film can be bent in certain degree according to the shape of a lithium battery, so that the heat conductive film can be tightly attached to an external surface of the lithium battery, thereby achieving a better heat dissipation effect.
Description
Technical field
The present invention relates to a kind of flexible heat conducting film based on functional group's Graphene reduction and preparation method, be a kind of Graphene
Heat conducting film, particularly to a kind of Flexible graphene membrane preparation method with heat conduction function.This heat conducting film can be pasted on battery
Outside in monomer, or it is wrapped in outside batteries, to improve the radiating efficiency of battery, reduce internal temperature of battery.
Background technology
In the last few years, along with mobile communication, the high speed development of portable electric appts, it was greatly promoted in electrochmical power source
The development of secondary cell.In the secondary battery, due to lithium ion battery have that voltage is high, volume is little, light weight, specific energy are high,
The advantages such as memory-less effect, pollution-free, self discharge is little, have extended cycle life, become the emphasis of secondary cell development.But, lithium
Battery is extremely sensitive for temperature, if be chronically at overheated in the environment of, then can significantly reduce the life-span of battery, seriously
Overheated, electrolyte decomposition, intrinsic pressure increase causes blast, even if not blast, battery also can be hankered scrapping rapidly at height.Cause
This, conduct the raising that will assist in battery safety and service life rapidly and uniformly by the heat that battery produces.
Graphite material belongs to nonmetal crystal material, and its heat conduction is mainly by the vibration of lattice, i.e. lattice wave (phonon) leads to
Mutually restriction and the mutually coordinated vibration of crossing crystal structure unit realize the conduction of heat.Graphene is to have carbon carbon sp2Miscellaneous
The carbon simple substance of the hexagonal lattice structure changed, forms big pi-conjugated key, and the mean free path of the phonon of Graphene is far longer than
High-heat conductivity graphite material on ordinary meaning and the phonon free path of other material, its phonon free path about 775 nm, through meter
Calculation can obtain the thermal conductivity of Graphene and be up to 5300 W/m K.Telescoping it addition, Graphene is internal under room temperature, wherein electronics is subject to
The interference arrived is the least, thus electronics freedom of movement, wherein the movement rate of electronics reaches the 1/300 of the light velocity, greatly exceed
Electronics movement rate in general conductor, under room temperature, electron mobility is up to 15000 cm2/ (V s), has exceeded any gold
The electron mobility belonged to.This exoelectron moves in electron orbit, will not scatter because of lattice defect or foreign atom.From
This respect is said, the heat conduction of Graphene is to be realized by The Wave Behavior of Electrons.Therefore, jointly act at phonon and two aspects of electronics
Under, make Graphene have outstanding heat conductivility.
Summary of the invention
It is an object of the invention to provide a kind of Flexible graphene heat conducting film, this heat conducting film can enter according to the profile of lithium battery
The a certain degree of bending of row, and then make it closely fit with lithium battery outer surface, to reach preferably radiating effect.
Further object is that the preparation that a kind of flexible heat conducting film based on functional group's Graphene reduction is provided
Method, it is by the method for vacuum filled by filtration repeatedly, makes graphene microchip embed in the hole of microporous filter membrane, and method is simple,
Prepared by the large area being beneficial to heat conducting film.
In order to achieve the above object, the technical scheme is that and be achieved in that:
A kind of Flexible graphene heat conducting film, it is characterised in that by weight percentage by 2% ~ 10% graphene microchip and 90% ~ 98%
Microporous filter membrane composition；Wherein graphene microchip is graphene oxide or nitrogen-doped graphene microplate, and thickness is 5 nm ~ 80
Nm, sheet footpath is 1 μm ~ 5 μm；
Microporous filter membrane is acetate fiber composite fibre microporous filter membrane, PP polypropylene filter, nylon66 fiber filter membrane, PVDF Kynoar
In filter membrane, PTFE politef hydrophilic film, PTFE politef hydrophobic membrane, BT glass fiber filter, PES polyethersulfone membranes
One；Aperture is 8 μm ~ 18 μm, a diameter of 25 mm ~ 400 mm.
The preparation method of a kind of Graphene flexibility heat conducting film, it is characterised in that concrete preparation process is as follows:
Use ultrasonic method, graphene oxide or nitrogen-doped graphene are scattered in solvent, this solvent be ultra-pure water water, N ~
In methyl pyrrolidone (NMP), dimethylformamide (DMF), oxolane (THF), ethylene glycol one or both and more than
Mixture, the concentration of dispersion liquid is 1 mg/ml ~ 10mg/ml.
Utilize centrifuge, be centrifuged processing 1 h ~ 5h, rotating speed by graphene oxide or nitrogen-doped graphene dispersion liquid
It is 1000 r/min ~ 3000r/min, removes precipitate.
Utilize Vacuum filtration device, graphene oxide centrifugal treating crossed by filter membrane or nitrogen-doped graphene dispersion
Liquid carries out multiple times of filtration, changes positive/negative of filter membrane every time and continues to filter, make graphene oxide or nitrogen-doped graphene ooze after filtering
Enter in the internal void of filter membrane, until dispersion liquid become clarification, filtering times is 10 times ~ 40 times.
The filter membrane being supported with graphene oxide or nitrogen-doped graphene is placed under 60 DEG C ~ 120 DEG C vacuum conditions and is dried
4h~8h。
Dried filter membrane is carried out under atmosphere protection high-temperature process.Wherein, protective atmosphere is nitrogen, argon, helium
One in gas, high-temperature process temperature is 200 DEG C ~ 600 DEG C, and handling duration is 4h ~ 8h.
The positive effect of the present invention is to have the Flexible graphene heat conducting film that filter membrane supports, and has the heat conductivity of excellence, machine
Tool intensity and pliability.Deformation can be curved according to the profile of lithium battery, closely fit with lithium battery outer surface, as Fig. 2-
Shown in 4.
Accompanying drawing explanation
Fig. 1 is Flexible graphene heat conducting film material object photo.
Fig. 2 is Flexible graphene heat conducting film actual application schematic diagram 1.
Fig. 3 is Flexible graphene heat conducting film actual application schematic diagram 2.
Fig. 4 is Flexible graphene heat conducting film actual application schematic diagram 3.
Detailed description of the invention
The present invention will be further described with embodiment below in conjunction with the accompanying drawings:
Embodiment 1
Utilize ultrasonic cell disruptor, graphene oxide is scattered in ultra-pure water according to the concentration of 2mg/ml, ultrasonic disperse
Shi Changwei 3h.By dispersion liquid centrifugal treating 1h, centrifuge speed is 1000r/min, removes bottom precipitation, takes supernatant.Use
Aperture is that the dispersion liquid that centrifugal treating is crossed by the acetate fiber filter membrane of 12 μm carries out positive/negative and alternately filters, and filtering times is 20
Secondary.Then, the filter membrane being supported with graphene oxide is placed in dried 5h under 80 DEG C of vacuum conditions.Finally, by dried
Filter membrane is 400 DEG C of process 5h under argon atmosphere is protected, and obtain Graphene flexibility heat conducting film 1, as shown in Figure 1.Graphene flexibility is led
Hotting mask 1 can be used for the heat radiation of the battery in battery pack monomer 2 being made up of 18650 type batteries, as in figure 2 it is shown, Graphene flexibility is led
Hotting mask 1 can be fitted in battery cell surface according to the distribution form of the battery cell 2 in set of cells with snakelike pattern.
Embodiment 2
Utilize ultrasonic cell disruptor, nitrogen-doped graphene is scattered in DMF according to the concentration of 5mg/ml, during ultrasonic disperse
A length of 4h.By dispersion liquid centrifugal treating 3h, centrifuge speed is 2000r/min, removes bottom precipitation, takes supernatant.Use hole
Footpath is that the dispersion liquid that centrifugal treating is crossed by the polypropylene filter of 14 μm carries out positive/negative and alternately filters, and filtering times is 30 times.So
After, the filter membrane being supported with nitrogen-doped graphene is placed in dried 6h under 90 DEG C of vacuum conditions.Finally, by dried filter membrane
Under nitrogen atmosphere is protected, 200 DEG C process 6h, obtain Graphene flexibility heat conducting film 1, as shown in Figure 1.Graphene flexibility heat conducting film 1
Can be used for the heat radiation of the battery in battery pack monomer 2 being made up of 18650 type batteries, as it is shown on figure 3, Graphene flexibility heat conducting film 1
Battery cell surface can be fitted in the pattern of S-shaped according to the distribution form of the battery cell 2 in set of cells.
Embodiment 3
Utilize ultrasonic cell disruptor, graphene oxide is scattered in THF according to the concentration of 8mg/ml, ultrasonic disperse duration
For 3h.By dispersion liquid centrifugal treating 4h, centrifuge speed is 3000r/min, removes bottom precipitation, takes supernatant.Use aperture
Being that the dispersion liquid that centrifugal treating is crossed by the PVDF Kynoar filter membrane of 16 μm carries out positive/negative and alternately filters, filtering times is
35 times.Then, the filter membrane being supported with graphene oxide is placed in dried 8h under 80 DEG C of vacuum conditions.Finally, will be dried
Filter membrane argon atmosphere protect under 400 DEG C process 7h, obtain Graphene flexibility heat conducting film 1, as shown in Figure 1.Graphene is flexible
Heat conducting film 1 can be used for the heat radiation of square battery cell 2, and as shown in Figure 4, Graphene flexibility heat conducting film 1 can be according to rectangular cell
External form be fitted tightly over battery cell surface.
Embodiment 4
Utilize ultrasonic cell disruptor, nitrogen-doped graphene is scattered in ethylene glycol according to the concentration of 10mg/ml, ultrasonic point
A length of 5h when dissipating.By dispersion liquid centrifugal treating 2h, centrifuge speed is 2500r/min, removes bottom precipitation, takes supernatant.Adopt
The dispersion liquid crossed centrifugal treating with the BT glass fiber filter that aperture is 18 μm carries out positive/negative and alternately filters, filtering times
It it is 40 times.Then, the filter membrane being supported with nitrogen-doped graphene is placed in dried 4h under 60 DEG C of vacuum conditions.Finally, will be dry
Filter membrane after dry is 200 DEG C of process 8h under helium atmosphere is protected, and obtain Graphene flexibility heat conducting film 1, as shown in Figure 1.
Claims (2)
1. a Flexible graphene heat conducting film, it is characterised in that by weight percentage by 2% ~ 10% graphene microchip and 90% ~
The microporous filter membrane composition of 98%；Wherein graphene microchip is graphene oxide or nitrogen-doped graphene microplate, and thickness is 5 nm ~ 80
Nm, sheet footpath is 1 μm ~ 5 μm；Microporous filter membrane is acetate fiber composite fibre microporous filter membrane, PP polypropylene filter, nylon66 fiber filter
Film, PVDF Kynoar filter membrane, PTFE politef hydrophilic film, PTFE politef hydrophobic membrane, BT glass fibre are filtered
One in film, PES polyethersulfone membranes；Aperture is 8 μm ~ 18 μm, a diameter of 25 mm ~ 400 mm.
2. the preparation method of a Graphene flexibility heat conducting film, it is characterised in that concrete preparation process is as follows:
Using ultrasonic method, graphene oxide or nitrogen-doped graphene are scattered in solvent, this solvent is ultra-pure water water, N ~ first
In base ketopyrrolidine (NMP), dimethylformamide (DMF), oxolane (THF), ethylene glycol one or both and above
Mixture, the concentration of dispersion liquid is 1 mg/ml ~ 10mg/ml；
Utilizing centrifuge, be centrifuged processing 1 h ~ 5h by graphene oxide or nitrogen-doped graphene dispersion liquid, rotating speed is
1000 r/min ~ 3000r/min, removes precipitate；
Utilizing Vacuum filtration device, graphene oxide or the nitrogen-doped graphene dispersion liquid centrifugal treating crossed by filter membrane are entered
Row multiple times of filtration, changes positive/negative of filter membrane every time and continues to filter, make graphene oxide or nitrogen-doped graphene penetrate into after filtering
In the internal void of filter membrane, until dispersion liquid become clarification, filtering times is 10 times ~ 40 times；
The filter membrane being supported with graphene oxide or nitrogen-doped graphene is placed under 60 DEG C ~ 120 DEG C vacuum conditions be dried 4h ~
8h；
Dried filter membrane is carried out under atmosphere protection high-temperature process；Wherein, during protective atmosphere is nitrogen, argon, helium
One, high-temperature process temperature is 200 DEG C ~ 600 DEG C, and handling duration is 4h ~ 8h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107645065A (en) * | 2017-09-08 | 2018-01-30 | 西安工程大学 | A kind of preparation method of onion carbon/MXene stratiform Wave suction composite materials |
| CN107720722A (en) * | 2017-10-27 | 2018-02-23 | 西安理工大学 | A kind of nitrogenous multi-stage porous Carbon Materials and its preparation method and application |
| CN107946082A (en) * | 2017-10-27 | 2018-04-20 | 西安理工大学 | A kind of preparation method and its usage of cigarette filter/graphene composite material |
| CN110066174A (en) * | 2019-04-30 | 2019-07-30 | 冯德远 | A kind of preparation method of Flexible graphene composite heat conduction film |
| CN110844902A (en) * | 2019-11-20 | 2020-02-28 | 常州富烯科技股份有限公司 | Graphite foam and preparation method thereof |
| CN113620711A (en) * | 2021-08-26 | 2021-11-09 | 江西宁新新材料股份有限公司 | Graphite high-thermal-conductivity film and preparation method thereof |
| CN114956066A (en) * | 2022-06-30 | 2022-08-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene composite heat-conducting film and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107645065A (en) * | 2017-09-08 | 2018-01-30 | 西安工程大学 | A kind of preparation method of onion carbon/MXene stratiform Wave suction composite materials |
| CN107720722A (en) * | 2017-10-27 | 2018-02-23 | 西安理工大学 | A kind of nitrogenous multi-stage porous Carbon Materials and its preparation method and application |
| CN107946082A (en) * | 2017-10-27 | 2018-04-20 | 西安理工大学 | A kind of preparation method and its usage of cigarette filter/graphene composite material |
| CN110066174A (en) * | 2019-04-30 | 2019-07-30 | 冯德远 | A kind of preparation method of Flexible graphene composite heat conduction film |
| CN110844902A (en) * | 2019-11-20 | 2020-02-28 | 常州富烯科技股份有限公司 | Graphite foam and preparation method thereof |
| CN113620711A (en) * | 2021-08-26 | 2021-11-09 | 江西宁新新材料股份有限公司 | Graphite high-thermal-conductivity film and preparation method thereof |
| CN114956066A (en) * | 2022-06-30 | 2022-08-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene composite heat-conducting film and preparation method thereof |
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