CN113956852A - Heat-conducting phase-change gel material, preparation method thereof and battery module - Google Patents
Heat-conducting phase-change gel material, preparation method thereof and battery module Download PDFInfo
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- CN113956852A CN113956852A CN202111183501.4A CN202111183501A CN113956852A CN 113956852 A CN113956852 A CN 113956852A CN 202111183501 A CN202111183501 A CN 202111183501A CN 113956852 A CN113956852 A CN 113956852A
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- C—CHEMISTRY; METALLURGY
- 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
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- 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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- 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
- H01M10/61—Types of temperature control
- H01M10/613—Cooling or keeping cold
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- H—ELECTRICITY
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- 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
- H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
- H01M10/625—Vehicles
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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
- H01M10/655—Solid structures for heat exchange or heat conduction
- H01M10/6556—Solid parts with flow channel passages or pipes for heat exchange
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/656—Means for temperature control structurally associated with the cells characterised by the type of heat-exchange fluid
- H01M10/6567—Liquids
- H01M10/6568—Liquids characterised by flow circuits, e.g. loops, located externally to the cells or cell casings
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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
- H01M10/659—Means for temperature control structurally associated with the cells by heat storage or buffering, e.g. heat capacity or liquid-solid phase changes or transition
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Abstract
The invention relates to the field of heat conduction materials, in particular to a heat conduction phase change gel material, a preparation method thereof and a battery module. The invention discloses a heat-conducting phase-change gel, wherein a phase-change material in the heat-conducting phase-change gel is fixed in a three-dimensional cross-linked network of organic silicon, and can not be separated out even if the phase-change material is heated into a liquid state. The heat-conducting phase-change gel has certain elasticity after room temperature curing, and has the functions of protection and cushioning. The heat-conducting phase-change gel has heat-conducting and phase-change performances, and under the condition of filling the heat-conducting filler with the same mass fraction, the heat-conducting filler is extruded more tightly by adding the phase-change material, so that more heat-conducting passages are formed, and the heat-conducting performance is improved. The heat-conducting phase-change gel can flow before being cured without crosslinking and can be cured at room temperature, so that the heat-conducting phase-change gel can be used as an interface material, can easily fill a gap between a liquid cooling pipeline and the outer wall of a battery, improves the heat transfer efficiency, simultaneously exerts the characteristic of good temperature equalization performance of the phase-change material, and provides thermal management for the battery in cooperation with a liquid cooling system.
Description
Technical Field
The invention relates to the field of heat conduction materials, in particular to a heat conduction phase change gel material, a preparation method thereof and a battery module.
Background
There are still many problems to be solved in electric vehicles. Only from the perspective of the battery pack, endurance and safety issues are the two most interesting issues for electric vehicles. Both of which are temperature sensitive.
Among others, one of the reasons affecting the endurance of the battery is the operating temperature. (addition) heat dissipation: the charge and discharge capacity of the battery is reduced at low temperature, energy and power are lost, and the capacity is even 10 percent of that at room temperature; meanwhile, a large amount of heat is generated during charging and discharging of the battery, and the optimal working temperature of the battery is 20-55 ℃. When the battery is heated, heat needs to be conducted out in time, otherwise, detonation can occur. 2. Temperature equalization: the temperature difference in the same battery pack cannot exceed 5 ℃, otherwise, the charge and discharge degrees of each battery are inconsistent, and the internal structure of the battery is damaged and the safety problem is caused due to the overcharge or overdischarge of individual batteries.
In summary, thermal management and certain external protection of the battery are essential.
There are three common ways of thermal management currently on the market and in research: air cooling, liquid cooling, and phase change materials. The liquid cooling structure is complex, can realize temperature reduction and temperature rise, has high temperature control efficiency and good effect, and is also a method for a plurality of vehicle enterprises. However, the liquid-cooled plate or the liquid-cooled tube is not always tightly attached to the battery due to macroscopic warpage and microscopic roughness, and the thermal contact resistance is formed by the gaps existing between the contact surfaces, so that the heat exchange efficiency is reduced. And the liquid cooling system can't guarantee that water inlet and delivery port temperature are unanimous or close, and this defect can cause everywhere battery temperature in same group battery to differ, and battery module specification is big more, and the difference in temperature is more obvious. The phase change material can keep constant temperature in a certain temperature range due to unique physical properties, and is an ideal material for battery thermal management. However, most of the existing heat conduction phase change materials are hard and solid, and cannot be well matched with complex gaps between the battery pack and the liquid cooling system.
Disclosure of Invention
In view of the above, the invention provides a heat-conducting phase-change gel material, a preparation method thereof and a battery module, wherein the heat-conducting phase-change gel material has heat-conducting and temperature-equalizing performances and is elastic; the phase-change material in the heat-conducting phase-change gel is wrapped in the three-dimensional cross-linked network of the organic silicon, and leakage cannot be generated. Therefore, the heat-conducting phase-change gel can well match complex gaps between the battery pack and the liquid cooling system.
The specific technical scheme is as follows:
the invention provides a heat-conducting phase-change gel material which is prepared from the following components in parts by weight:
10-100 parts of heat-conducting filler;
10-100 parts of phase change material;
100 parts of polysiloxane;
0.001-10 parts of a crosslinking inhibitor;
0.0001-0.01 part of catalyst.
According to the invention, the heat-conducting phase-change gel material contains the organic silicon gel, and the heat-conducting phase-change gel contains the organic silicon gel with a three-dimensional cross-linked network structure, so that the phase-change material is fixed in the three-dimensional cross-linked network, and even if the phase-change material is heated to be in a liquid state, the phase-change material cannot be separated out to damage the protection performance of the material. In addition, the heat-conducting phase-change gel can be solidified at room temperature, has certain elasticity after being solidified, and has the functions of protection and shock absorption. In addition, the heat-conducting phase-change gel has heat-conducting and phase-change performances, and under the condition that the heat-conducting filler with the same mass fraction is filled, the heat-conducting filler is extruded more tightly by adding the phase-change material, so that more heat-conducting passages are formed, and the effects of improving the heat-conducting performance and saving the cost are achieved. After the gel is solidified, the heat conduction path is fixed in the polymer matrix and is not changed due to the fact that the phase change material is heated and liquefied.
In the present invention, the thermally conductive filler includes: a metal, ceramic or carbon material; wherein the metal is one or more than two of copper, aluminum and silver; the ceramic is one or more than two of silicon carbide, silicon nitride, silicon dioxide, boron nitride and aluminum nitride; the carbon material is one or more than two of graphite, expanded graphite, graphene and carbon nano tubes.
The phase-change temperature range of the phase-change material is 20-70 ℃, and the heat-conducting phase-change gel has temperature-equalizing performance. In the invention, the phase-change material is paraffin or organic silicon wax.
The polysiloxane comprises: one or more of vinyl polysiloxane, terminal (side) hydrogen polysiloxane and alpha, omega-dihydroxy polysiloxane;
the crosslinking inhibitor includes: one or more of esters, alcohols, sulfur, nitrogen-containing derivatives and alkynes; the esters are preferably tetraethyl orthosilicate, maleate and fumarate; the alcohol is preferably ethynyl cyclohexanol; the sulfur is preferably an organic sulfoxide; the nitrogenous derivative is preferably acrylonitrile; the alkyne is preferably acetylene or phenylacetylene.
In the invention, when the polysiloxane is vinyl polysiloxane and hydrogen-terminated polysiloxane, the mass ratio of the vinyl polysiloxane to the hydrogen-terminated polysiloxane is 1: 0.01-1: 0.1.
The invention also provides a preparation method of the heat-conducting phase-change gel, which comprises the following steps:
and stirring and mixing the heat-conducting filler, the phase-change material and the polysiloxane, then adding the catalyst and the crosslinking inhibitor, stirring and mixing, and curing to obtain the heat-conducting phase-change gel.
The preparation method of the heat-conducting phase-change gel material provided by the invention is simple to operate and is suitable for industrial production.
In the invention, the crosslinking inhibitor is used for reducing the low-temperature catalytic activity of the catalyst and prolonging the reaction time, and the catalyst can quickly recover the activity under the high-temperature condition.
In the invention, the catalyst is lithium hydroxide or a platinum liquid catalyst, and the platinum liquid catalyst is preferably chloroplatinic acid;
the curing temperature is room temperature; the room temperature was 25. + -. 5 ℃.
The invention also provides application of the heat-conducting phase-change gel in a battery module.
The heat-conducting phase-change gel material provided by the invention can flow before being cured without crosslinking because of the interface material with heat-conducting and phase-change properties, and can be cured at room temperature. The liquid cooling system can easily fill the gap between the liquid cooling pipeline and the outer wall of the battery, improves the heat transfer efficiency, simultaneously exerts the characteristic of good temperature equalization performance of the phase change material, and provides the battery heat management in cooperation with the liquid cooling system.
The invention also provides a battery module, which comprises a battery, a liquid cooling system and the heat-conducting phase-change gel material;
the heat conduction phase change gel material is arranged between a liquid cooling pipeline of the liquid cooling system and the battery.
According to the technical scheme, the invention has the following advantages:
the invention provides a heat-conducting phase-change gel material, which is characterized in that the heat-conducting phase-change gel material contains organic silicon gel with a three-dimensional cross-linked network structure, and the phase-change material is fixed in the three-dimensional cross-linked network, so that the phase-change material cannot be separated out to damage the protection performance of the material even if the phase-change material is heated into a liquid state. In addition, the heat-conducting phase-change gel can be cured at room temperature, has certain elasticity after being cured, and has the functions of protection and shock absorption. In addition, the heat-conducting phase-change gel has heat-conducting and phase-change performances, and under the condition of filling the heat-conducting filler with the same mass fraction, the heat-conducting filler is extruded more tightly by adding the phase-change material, so that more heat-conducting passages are formed, and the effects of improving the heat-conducting performance and saving the cost are achieved. After the gel is solidified, the heat conduction path is fixed in the polymer matrix and is not changed due to the fact that the phase change material is heated and liquefied. Since the thermally conductive phase change gel is flowable before being cured without crosslinking, it is curable at room temperature. The heat-conducting phase-change material can be used as an interface material, can easily fill a gap between a liquid-cooling pipeline and the outer wall of a battery, improves the heat transfer efficiency, simultaneously exerts the characteristic of good temperature uniformity of the phase-change material, and provides heat management for the battery in cooperation with a liquid-cooling system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a thermally conductive phase change gel prepared in example 1 of the present invention;
FIG. 2 is a diagram of a material for a compression bend resistance test of a thermally conductive phase change gel according to an example of the present invention;
FIG. 3 is a diagram of an anti-leakage test object of a phase change material performed in an experimental example of the present invention;
fig. 4 is a diagram illustrating a temperature test of charging and discharging the battery module by using the heat-conducting phase-change gel according to the experimental example of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The embodiment is a preparation method of a heat-conducting phase-change gel, and the preparation method comprises the following specific preparation steps in parts by weight:
mixing 40 parts of vinyl siloxane, 10 parts of hydrogen-terminated siloxane and 0.001 part of ethynyl cyclohexanol fully; adding 40 parts of paraffin and 10 parts of boron nitride, stirring to fully mix, stirring in vacuum by a planetary stirrer (the stirring speed is 100 revolutions per minute, and the stirring time is 4 hours), then adding 0.004 part of chloroplatinic acid, continuously stirring uniformly, and curing at room temperature to obtain the heat-conducting phase-change gel.
Fig. 1 is a scanning electron microscope image of the thermally conductive phase change gel prepared in example 1 of the present invention. It can be seen from fig. 1 that the heat conductive filler and the paraffin particles are uniformly dispersed in the heat conductive phase change gel, and the presence of the paraffin particles makes the heat conductive filler more tightly stacked, so as to form more heat conductive paths.
Example 2
The embodiment is a preparation method of a heat-conducting phase-change gel, and the preparation method comprises the following specific preparation steps in parts by weight:
mixing 40 parts of vinyl siloxane, 10 parts of hydrogen-terminated siloxane and 0.001 part of ethynyl cyclohexanol fully; adding 40 parts of organic silicon wax and 10 parts of boron nitride, stirring to fully mix, stirring in vacuum by a planetary stirrer (the stirring speed is 100 revolutions per minute, and the stirring time is 4 hours), then adding 0.008 part of chloroplatinic acid, continuously stirring uniformly, and curing at room temperature to obtain the heat-conducting phase-change gel.
Example 3
The embodiment is a preparation method of a heat-conducting phase-change gel, and the preparation method comprises the following specific preparation steps in parts by weight:
fully mixing 50 parts of alpha, omega-dihydroxy polysiloxane and 0.001 part of trace ethynyl cyclohexanol; adding 40 parts of paraffin and 10 parts of boron nitride, stirring to fully mix, stirring in vacuum by a planetary stirrer (the stirring speed is 100 revolutions per minute, and the stirring time is 4 hours), then adding 0.005 part of lithium hydroxide, continuously stirring uniformly, and curing at room temperature to obtain the heat-conducting phase-change gel.
Comparative example 1
The comparative example is the preparation of pure silica gel, and comprises the following specific preparation steps in parts by weight:
mixing 80 parts of vinyl siloxane, 20 parts of terminal hydrogen siloxane and 0.002 part of ethynyl cyclohexanol fully, stirring under vacuum by a planetary stirrer (the stirring speed is 100 r/min, the stirring time is 4 hours), and then adding 0.008 part of chloroplatinic acid catalyst to obtain pure silica gel.
Comparative example 2
The comparative example is the preparation of the boron nitride/silica gel composite material, and the preparation steps are as follows according to parts by mass:
fully mixing 10 parts of boron nitride, 72 parts of vinyl siloxane, 18 parts of terminal hydrogen siloxane and 0.002 part of ethynyl cyclohexanol, stirring under vacuum by a planetary stirrer (the stirring speed is 100 revolutions per minute, and the stirring time is 4 hours), and then adding 0.008 part of chloroplatinic acid catalyst to obtain the boron nitride/silica gel.
Test examples
1. The thermally conductive phase change gel prepared in example 1, the pure silica gel prepared in comparative example 1, the boron nitride/silica gel composite material prepared in comparative example 2, and the pure paraffin were subjected to extrusion resistance, bending resistance, and leakage resistance tests.
The impact resistance test is performed by placing a sample in a universal testing machine, pressing the sample downward at a speed of 50mm/min, and detecting a pressure probe and displacement data.
The bending resistance test is to bend and rotate and twist the sample strips by hands.
The anti-leakage test is that samples with the same specification are simultaneously placed in an oven at 80 ℃, taken out at intervals, weighed and photographed, and the leakage and mass loss conditions are recorded.
As shown in fig. 2, the heat-conducting phase-change gel is extruded and bent to a certain extent, and the material can recover the original shape, which indicates that the heat-conducting phase-change gel can play a certain role in protecting the battery module after being filled in the battery module.
As shown in fig. 3, the heat-conducting phase-change gel and the phase-change material pure paraffin were placed in a 60 ℃ incubator, and five minutes later, the pure paraffin had leaked, while the heat-conducting phase-change gel did not leak any more within 72 hours.
2. The thermally conductive phase change gel prepared in example 1 was applied to a battery module.
As shown in fig. 4, the maximum temperature of the battery No. 6 without the thermal conductive phase change gel (TCPCSG) reached 58.8 ℃ and 64.1 ℃ during charge and discharge, while the maximum temperature of the battery No. 6 loaded with the thermal conductive phase change gel of example 1 reached 45.0 ℃ and 56.9 ℃ during charge and discharge, and decreased by 13.8 ℃ and 7.2 ℃, respectively, and the temperature decrease effect was significant. Meanwhile, by deriving the temperature rise curve, it can be seen that the TCPCSG smoothes the rate of change of the battery temperature.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The heat-conducting phase-change gel material is characterized by comprising the following raw materials in parts by mass:
10-100 parts of heat-conducting filler;
10-100 parts of phase change material;
100 parts of polysiloxane;
0.001-10 parts of a crosslinking inhibitor;
0.0001-0.01 part of catalyst.
2. The thermally conductive phase change gel material of claim 1, wherein the thermally conductive filler comprises: a metal, ceramic or carbon material;
the phase change temperature range of the phase change material is 20-70 ℃;
the polysiloxane comprises: one or more of vinyl polysiloxane, terminal (side) hydrogen polysiloxane and alpha, omega-dihydroxy polysiloxane;
the crosslinking inhibitor includes: one or more than two of esters, alcohols, ketones, sulfonamides, phosphates, phosphoric acid, nitrogenous derivatives, peroxides and alkynes.
3. The thermally conductive phase change gel material of claim 2, wherein the phase change material is a paraffin or silicone wax.
4. The heat-conducting phase-change gel material as claimed in claim 1, wherein when the polysiloxane is vinyl polysiloxane and hydrogen-terminated polysiloxane, the mass ratio of the vinyl polysiloxane to the hydrogen-terminated polysiloxane is 1: 0.01-1: 0.1.
5. The thermally conductive phase change gel material of claim 2, wherein the metal is one or more of copper, aluminum, and silver;
the ceramic is one or more than two of silicon carbide, silicon nitride, silicon dioxide, boron nitride and aluminum nitride;
the carbon material is one or more than two of graphite, expanded graphite, graphene and carbon nano tubes.
6. The thermally conductive phase change gel material of claim 1, wherein the catalyst is a lithium hydroxide or platinum liquid catalyst.
7. The method for preparing a heat-conducting phase-change gel material as claimed in any one of claims 1 to 6, comprising the steps of:
and stirring and mixing the heat-conducting filler, the phase-change material and polysiloxane, adding a catalyst and a crosslinking inhibitor, stirring and mixing, and curing to obtain the heat-conducting phase-change gel.
8. The method according to claim 7, wherein the curing temperature is room temperature.
9. Use of the thermally conductive phase change gel material of any one of claims 1 to 6 in a battery module.
10. A battery module, comprising: a battery, a liquid cooling system, and the thermally conductive phase change gel material of any one of claims 1 to 6;
the heat conduction phase change gel material is arranged between a liquid cooling pipeline of the liquid cooling system and the battery.
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| CN114497813A (en) * | 2022-03-31 | 2022-05-13 | 深圳市森若新材科技有限公司 | Phase change composite film, and battery and chip assembly including the same |
| CN114686017A (en) * | 2022-04-15 | 2022-07-01 | 苏州高泰电子技术股份有限公司 | Phase change energy storage heat conduction material and preparation process thereof |
| CN116113217A (en) * | 2023-02-18 | 2023-05-12 | 广东工业大学 | Flexible heat-conducting ionic liquid phase-change gel material and preparation method and application thereof |
| CN117004231A (en) * | 2023-08-24 | 2023-11-07 | 常州宏巨电子科技有限公司 | Low-volatility quick-curing phase-change heat-conducting gasket and preparation method thereof |
| CN117410627A (en) * | 2023-11-18 | 2024-01-16 | 武汉现代精工机械股份有限公司 | Solid superconducting material for lithium battery and lithium battery thermal management system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114497813A (en) * | 2022-03-31 | 2022-05-13 | 深圳市森若新材科技有限公司 | Phase change composite film, and battery and chip assembly including the same |
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