CN116462954A - Dual-network battery thermal management material and preparation method thereof - Google Patents
Dual-network battery thermal management material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000945 filler Substances 0.000 claims abstract description 36
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- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 16
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 15
- 229910052582 BN Inorganic materials 0.000 claims description 13
- 229920002678 cellulose Polymers 0.000 claims description 12
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- 239000002135 nanosheet Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229910003460 diamond Inorganic materials 0.000 claims description 8
- 239000010432 diamond Substances 0.000 claims description 8
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 230000009977 dual effect Effects 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011231 conductive filler Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000017525 heat dissipation Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
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- 239000012782 phase change material Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 3
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- 229920001046 Nanocellulose Polymers 0.000 description 2
- 230000003139 buffering effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000110 cooling liquid Substances 0.000 description 1
- 239000013039 cover film Substances 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
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- 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 the field of battery thermal management materials, and particularly discloses a double-network battery thermal management material, which comprises a first heat conduction composite network, a second heat conduction composite network and a heat exchange composite network, wherein the first heat conduction composite network comprises a high polymer matrix material and an anisotropic heat conduction filler; the first and second heat conductive networks are interposed. The preparation method of the dual-network battery thermal management material has the advantages of higher thermal conductivity, higher thermal storage capacity and excellent insulating property. The invention also provides a preparation method of the dual-network battery thermal management material.
Description
Technical Field
The invention belongs to the field of battery thermal management materials, and particularly relates to a dual-network battery thermal management material and a preparation method thereof.
Background
In order to meet the increasing endurance demands of new energy automobiles, the power density of batteries is increased, and higher requirements are put forward to the problems of heat dissipation and heat storage of the batteries. It is therefore important to design efficient thermal management materials.
The traditional heat dissipation material of the heat dissipation battery is usually a metal composite plate, and Chinese patent No. CN202110203413.X discloses a battery heat management device and a control method, and mainly comprises a cooling liquid, a heat pipe hot end, a multi-layer heat insulation component, a heat pipe middle section and a heat pipe cold end; the device mainly comprises a thermal management device, a thermal management water outlet pipeline, a water pump, each branch control valve, each battery pack control valve of a single branch and a thermal management water return pipeline. The heat dissipation power of the battery is regulated by the control circuit, and the method belongs to a passive heat treatment process. And aluminum heat sink covers as used in the above patents. However, in the application, the application of the conventional packaging material is limited due to the conditions of insulation, flexibility and the like required for the packaging of the battery element.
In recent years, a high heat conduction material is prepared to encapsulate a high power battery by adding a high heat conduction filler to a polymer through polymer nano engineering. These nanofillers have ultra-high thermal conductivity because scattering of phonons or electrons is limited and ultra-high phonon or electron velocities are obtained. For example, the thermal conductivity of diamond reaches 1000-5000 W.m -1 ·K -1 The in-plane thermal conductivity of the boron nitride nano-sheet reaches 2000 W.m -1 ·K -1 And the boron nitride nano-sheet and the diamond have excellent electrical insulation property and low dielectric constant, and the properties can lead the material to be applied to the field of complex and high-energy integrated circuit battery thermal management. Thus, boron nitride nanoplatelets have gained academic and industrial interest.
The Chinese patent with the patent publication number of CN109627471A discloses a preparation method and application of a high-heat-conductivity flexible film, BNNS with high heat conductivity is hydroxylated to prepare dispersion liquid, nanocellulose is dispersed to prepare dispersion liquid, then hydroxylated boron nitride dispersion liquid is mixed with the dispersion liquid of cellulose to obtain uniform dispersion liquid, finally, moisture is removed by a vacuum auxiliary filtration self-assembly method, boron nitride sheets are regularly arranged, and finally, the hydroxylated boron nitride nanocellulose heat dissipation film is obtained after drying at room temperature, but the cover film has a certain uniform heat effect on high heat conductivity in the surface, has poor heat dissipation effect, is still weak in high heat dissipation caused by a battery instability event facing high power density, and does not have heat buffering capability on sudden temperature rise of a battery.
Therefore, it is needed to design a battery with high heat transfer performance, and the enne has high latent heat performance, so that the battery temperature can be absorbed and buffered in time in the face of sudden high heat, and the efficient thermal management of the battery is realized.
Disclosure of Invention
In view of the above, the present invention aims to: a dual network battery thermal management material having high thermal conductivity and high latent heat performance is provided.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: providing a double-network battery thermal management material and a preparation method thereof; the double-network battery thermal management material comprises a first heat conduction composite network and a second heat conduction composite network, wherein the first heat conduction composite network comprises a high polymer matrix material and anisotropic heat conduction filler; the second heat conduction composite network comprises isotropic heat conduction filler and a high polymer matrix material, and the second heat conduction network is inserted in the first heat conduction composite network.
The anisotropic heat conduction filler is in a net structure.
The anisotropic heat conduction filler is a two-dimensional material, preferably graphene, boron nitride nanosheets and aluminum oxide sheets.
The heat conducting filler adhesive is a polymer matrix material, and aqueous polymers such as cellulose, polyvinyl alcohol and the like are selected.
The isotropic heat conductive filler is alumina, diamond or magnesia.
The filling matrix is made of phase-change polymer materials such as paraffin, polyethylene glycol and the like.
The particle size of the anisotropic heat conduction filler is 3-15 mu m, the size and thickness of the filler are too large, the three-dimensional network structure is difficult to construct, the heat conductivity of the material is reduced, the contact surface is fewer when the size is too small, and the contact thermal resistance among the fillers is increased, so that the heat conductivity of the material is reduced.
The particle size of the isotropic heat conduction filler is 0.3-1.5 mu m, the filler is oversized, and the filler cannot be uniformly mixed with high polymer materials such as polyethylene glycol, paraffin and the like and poured into a first network, so that the inside of the material is left porous, and the heat conductivity of the material is reduced; too small a material size introduces more interfacial thermal resistance and also reduces the thermal conductivity of the material.
Furthermore, the isotropic heat conducting filler is spherical alumina or spherical diamond-like powder, the anisotropic heat conducting filler is boron nitride nanosheets or aluminum oxide sheets, and the viscosity of the heat conducting filler after being mixed with a polymer cannot be excessively high and the heat conducting filler needs to have certain fluidity.
According to the invention, by constructing a three-dimensional heat conduction network of the anisotropic two-dimensional material, an accurate heat conduction network is constructed in the material, so that heat soaking and rapid conduction are realized; in addition, the stability of the three-dimensional structure ensures that the composite material has better shape stability when absorbing heat; according to the invention, the isotropic heat conduction filler is mixed with the phase change material and then poured into the three-dimensional network, so that an isotropic second heat conduction path is constructed, and meanwhile, the phase change material is encapsulated, so that the phase change material can be quickly absorbed when facing high heat generated by instability of the battery, and the heat management efficiency of the battery is improved.
The invention also provides a preparation method of the dual-network battery thermal management material, which comprises the following specific operations:
(1) Mixing the anisotropic heat conduction filler with the adhesive solution, and performing ultrasonic treatment to obtain a mixed solution A;
(2) Placing the mixed solution A in a polytetrafluoroethylene mould, freezing the mixed solution A to form blocks below-50 ℃, and freeze-drying the blocks in a freeze dryer to obtain a preform C, wherein the freeze-drying time is 48h less than 25 Pa;
(3) Mixing isotropic heat conduction filler with a filling matrix, then adopting vacuum impregnation, and filling into a preform C to obtain a double-network battery heat management material;
the height of the die is 1-3 cm, and the thickness of the preform is 1-3 cm.
In the step (1), the mass ratio of the anisotropic heat conduction filler to the matrix is 7:1-9.5:1.
In the step (3), the mass ratio of the isotropic heat conduction filler to the matrix is 0.5:1-3:1.
A surface modifier, either dopamine or epichlorohydrin, can be added during the ultrasound process for preparing the mixed solution.
The surface modifier is not more than 0.1 wt% in the mixed solution A.
By adopting a freeze-drying method, the anisotropic heat conduction filler can be connected into a network structure, and compared with direct mixing, the material has higher heat conductivity.
Compared with the prior art, the invention has the beneficial effects that:
(1) The battery thermal management material prepared by the invention firstly builds a three-dimensional heat conduction network, improves the heat transfer efficiency of the material, builds a second heat conduction network by adopting a pouring method and isotropic heat conduction filler, and fills up a heat conduction passage between the heat conduction filler based on the bridging connection effect of the out-of-plane anisotropic heat conduction filler and the in-plane isotropic heat conduction filler double network, thereby having higher heat conductivity in the longitudinal direction. The thermal conductivity of the film prepared by the invention is 5-10 W.m -1 ·K -1 ；
(2) The invention reduces leakage of the battery thermal management material based on the packaging effect of the double network on the phase change material, so that the battery thermal management material has higher latent heat performance, thereby achieving the purposes of better buffering effect and timely absorbing heat when the battery thermal management material prepared by the invention faces high temperature, and the latent heat of the prepared battery thermal management material is 111.7-180.5 J.g -1 Breaking while maintaining 1000 cycle tests, maximum volume resistance of 5×10 13 Ω·cm。
Detailed Description
The present invention measures the thermal conductivity of the dual network battery thermal management materials prepared in the various examples by ASTM E1461-2013 test methods; the volume resistance of the dual network battery thermal management materials prepared in the various examples was measured by GBT 228-2002; the latent heat of the dual network battery thermal management material prepared in each example was measured by the DB61/T1090-2017B method.
Example 1
Raw materials: 0.5g of cellulose is dispersed in water to form 50-g g of cellulose (1-wt%) solution, 0.7-1.5 g of boron nitride nano-sheet, 2-3 g of alumina balls and 100g of polyethylene glycol.
Firstly, uniformly mixing 10g of cellulose solution, 0.9 and g of boron nitride nano-sheet and 10mL of water, performing ultrasonic treatment in a water bath of 150W for 30 min, uniformly mixing a solution A, and pouring the solution A into a polytetrafluoroethylene mold to form gel; and then placing the polytetrafluoroethylene mould filled with the solution A in a low-temperature bath at the temperature of-70 ℃ to be frozen into blocks, and finally, placing the frozen polytetrafluoroethylene mould in a freeze dryer to be freeze-dried for 48 hours under 25 Pa to obtain a preform B.
100g of polyethylene glycol is melted at 85 ℃, 2g of alumina is added and mixed to obtain suspension C, the prefabricated body B is immersed in the suspension C in vacuum, and the vacuum is pumped for 5 hours to obtain the dual-network battery thermal management material. The thermal conductivity of the material is 7.5 W.m -1 ·K -1 At the same time, 1000-cycle stack test can be maintained, and the volume resistance is 3.7X10 13 Ω·cm。
Example 2
Raw materials: 0.5g of cellulose is dispersed in water to form 50-g of cellulose (1-wt%) solution, 0.7-1.5 g of boron nitride nano-sheet, 2-3 g of diamond and 100g of paraffin.
Firstly, uniformly mixing 10g of cellulose solution, 0.9 and g of boron nitride nano-sheet and 10mL of water, performing ultrasonic treatment in a water bath of 150W for 30 min, uniformly mixing a solution A, and pouring the solution A into a polytetrafluoroethylene mold to form gel; and then placing the polytetrafluoroethylene mould filled with the solution A in a low-temperature bath at the temperature of-70 ℃ to be frozen into blocks, and finally, placing the frozen polytetrafluoroethylene mould in a freeze dryer to be freeze-dried for 48 hours under 25 Pa to obtain a preform B.
100g of paraffin wax is melted at 55 ℃, 2g of diamond is added to obtain suspension C after mixing, the prefabricated body B is immersed in the suspension C in vacuum, and the vacuum is pumped for 5 hours to obtain the dual-network battery thermal management material. The thermal conductivity of the material is 8.5 W.m -1 ·K -1 At the same time, 1000-cycle stack test can be maintained, and the volume resistance is 5 multiplied by 10 13 Ω·cm。
Comparative example 1
Raw materials: 0.5g of cellulose is dispersed in water to form 50-g of cellulose (1-wt%) solution, 0.7-1.5 g of boron nitride nano-sheet, 2-3 g of diamond and 100g of polyethylene glycol.
Firstly, uniformly mixing 10g of cellulose solution, 0.9 g g of boron nitride nano-sheet and 10g of water to obtain suspension A, and then heating the suspension A to 80 ℃ for later use; and then 100g of polyethylene glycol is melted in an oven at 80 ℃, 3g of diamond powder is added to obtain suspension B, and the A and the B are mixed and cooled to obtain the common battery thermal management material.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (6)
1. A dual network battery thermal management material, comprising:
the first heat conduction composite network comprises a high polymer matrix material and anisotropic heat conduction filler;
the second heat conduction composite network comprises isotropic heat conduction filler and a high polymer matrix material, and is inserted in the first heat conduction composite network;
the anisotropic heat conduction filler is in a net structure;
the anisotropic heat conduction filler is any one of graphene, boron nitride nano-sheets and aluminum oxide sheets;
the polymer matrix material is cellulose, polyvinyl alcohol is a heat-conducting filler adhesive, and polyethylene glycol and paraffin are filling matrixes;
the isotropic heat conduction filler is any one of alumina, diamond or magnesia.
2. The dual network battery thermal management material of claim 1, wherein the anisotropic conductive filler has a particle size of 3-15 μm.
3. The dual network battery thermal management material of claim 1, wherein the particle size of the isotropic thermally conductive filler is 0.5-1.5 μm.
4. The method for preparing the dual-network battery thermal management material according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the anisotropic heat conduction filler with the adhesive solution, and performing ultrasonic treatment to obtain a mixed solution A;
(2) Placing the mixed solution A in a polytetrafluoroethylene mould, freezing the mixed solution A to form blocks below-50 ℃, and freeze-drying the blocks in a freeze dryer to obtain a preform C, wherein the freeze-drying time is 48h less than 25 Pa;
(3) And mixing the isotropic heat conduction filler with the filling matrix, then adopting vacuum impregnation, and filling the mixture into the prefabricated body C to obtain the double-network battery heat management material.
5. The method for preparing a dual-network battery thermal management material according to claim 4, wherein in the step (1), the mass ratio of the anisotropic heat conductive filler to the adhesive is 7:1-9.5:1.
6. The method for preparing a dual-network battery thermal management material according to claim 4, wherein in the step (3), the mass ratio of the isotropic heat conductive filler to the filler matrix is 0.5:1-3:1.
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| CN202310700055.2A CN116462954A (en) | 2023-06-14 | 2023-06-14 | Dual-network battery thermal management material and preparation method thereof |
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