CN108084957B - Heat-conducting and heat-storing multifunctional encapsulating silica gel and preparation method thereof - Google Patents
Heat-conducting and heat-storing multifunctional encapsulating silica gel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a heat-conducting heat-storing multifunctional encapsulating silica gel and a preparation method thereof, wherein the heat-conducting heat-storing multifunctional encapsulating silica gel consists of 40-89% of bi-component encapsulating silica gel, 5-20% of phase change microcapsule, 5-20% of heat-conducting filler subjected to surface treatment and 1-20% of flame retardant in percentage by mass; the heat-conducting filler is formed by mixing small-particle-size heat-conducting filler and large-particle-size heat-conducting filler. The preparation method comprises the following steps: surface treatment of the heat-conducting filler; preparing a heat-conducting heat-storing composite filler; preparing two-component encapsulating silica gel; preparing A1 and B1 components in the heat-conducting heat-storing multifunctional encapsulating silica gel; and preparing the heat-conducting and heat-storing multifunctional encapsulating silica gel. The heat-conducting heat-storing multifunctional encapsulating silica gel adopts the heat-conducting filler with different grain diameters for surface treatment, the dispersibility of the heat-conducting filler in a silica gel matrix is increased, the heat-conducting property of the heat-conducting heat-storing multifunctional encapsulating silica gel is improved, and the phase-change microcapsule is added, so that the heat-conducting heat-storing multifunctional encapsulating silica gel has the heat-storing temperature-controlling property.
Description
Technical Field
The invention relates to the technical field of battery thermal management, in particular to heat-conducting and heat-storing multifunctional encapsulating silica gel and a preparation method thereof.
Background
Batteries, such as secondary batteries, have been widely used as energy sources for wireless mobile devices, for example, as power sources for electric vehicles, hybrid electric vehicles, and plug-in hybrid electric vehicles, etc., in order to solve problems, such as air pollution, caused by vehicles using petroleum fuel, small-sized wireless mobile devices may use one or more battery cells, while medium-or large-sized wireless devices, such as vehicles, may use medium-or large-sized battery modules including a plurality of battery cells connected to each other, such medium-or large-sized battery modules being generally manufactured to have as small a size and weight as possible, and thus the integration degree of the battery cells stacked in the battery modules is very high.
During the charge and discharge of the battery, the battery generates a large amount of heat. Particularly, the thermally conductive polymer material, on the surface of which the battery module is often coated, it is difficult to effectively reduce the overall temperature of the battery cell. If the heat generated from the battery module during the charge and discharge is not effectively removed, the heat is accumulated in the battery module, resulting in accelerated degradation of the battery module and reduced service life. Sometimes the battery module may even catch fire or explode, among other safety-related events. Thermal management of the battery is generally required to control the operating ambient temperature of the battery.
Currently, thermal management systems for batteries are generally classified into air cooling and liquid cooling. Air cooling is the method mainly adopted at present, and is easy to realize, but the cooling effect is poor. The liquid cooling radiating effect is better, but the structure is complicated, and the cost is higher, and the coolant leaks easily, and the reliability is poor.
The heat-conducting encapsulating silica gel is flame-retardant and heat-conducting double-component addition type organic silicon encapsulating silica gel, can be cured at room temperature and quickly cured by heating, has good insulating, shockproof, water-resistant, ozone-resistant and aging-resistant performances, can effectively prevent water vapor from permeating, and minimizes the adverse effect of external factors. The encapsulating protection method is widely applied to encapsulating protection of module power supplies and circuit boards which have high power electronic components and have high requirements on heat dissipation and temperature resistance. Such as waterproof, heat dissipation, buffering embedment of new energy automobile power lithium cell, solar panel, electronic components.
The traditional organic silicon encapsulating material has poor heat conduction capability, and can cause the difficulty in heat conduction and untimely heat dissipation during the working of equipment while protecting, so that local high temperature is formed, and the normal working of the equipment is further influenced, and even safety accidents are caused.
Phase Change Materials (PCMs) refer to a smart material in which a substance undergoes a phase change to enable the substance to absorb or emit heat without or without a substantial change in the temperature of the substance itself. Due to the unique functions of self-adaptive environmental temperature regulation and control and the like, the solar energy heat-storage air conditioner is widely applied to the fields of energy sources, materials, aerospace, textiles, electric power, medical instruments, building energy conservation and the like, such as solar energy utilization, industrial waste heat and waste heat recovery, building energy conservation, constant-temperature clothing, cold and heat storage air conditioners, constant temperature of electric devices and the like. Therefore, phase change materials are proposed to be applied to the thermal management system of the power battery.
Chinese patent application No. 201510414903.9 discloses a heat-conducting silica gel composite phase-change material, comprising: A) 50% -80% of heat-conducting silica gel, which is common AB bi-component organic silicon encapsulating silica gel; B) 20-50% of phase-change composite material which is paraffin wax with the temperature of 35-55 ℃; C) 0-20% of heat conducting agent which is expanded graphite; and D) 0-20% of flame retardant which is one or more of antimony trioxide, magnesium hydroxide and aluminum hydroxide, wherein the heat-conducting silica gel, the phase-change material, the heat-conducting agent and the flame retardant are uniformly mixed, evacuated in vacuum and cured and formed. However, the heat conducting agent in the phase-change composite material in the patent application is expanded graphite, the adsorption capacity of the expanded graphite to the phase-change material is limited, and the repeated use can cause serious problems of melt flow and infiltration migration of the phase-change material; in addition, the expanded graphite heat-conducting filler can seriously affect the insulating property of the encapsulating silica gel, is not beneficial to encapsulating application in conductive occasions, is used as a heat management system of the power battery, has great influence on the overall safety and reliability of the power battery, and is not suitable for popularization and application; secondly, the heat conducting agent used in the heat conducting silica gel in the patent application is alumina and magnesia, which are not subjected to surface treatment, and the directly added filler has poor compatibility with the silica gel matrix, so that the uniform dispersibility of the heat conducting filler in the silica gel matrix is reduced, the thermal resistance at the phase interface between the filler and the matrix is increased, and the heat conducting performance is reduced.
Disclosure of Invention
In order to solve one or more technical problems, the invention provides the heat-conducting heat-storing multifunctional encapsulating silica gel with good heat-conducting filler and silica gel matrix dispersibility, good insulativity, good heat-conducting property and heat-storing temperature-controlling property and the preparation method thereof.
The invention provides heat-conducting heat-storing multifunctional encapsulating silica gel in a first aspect, which consists of 40-89% of bi-component encapsulating silica gel, 5-20% of phase-change microcapsule, 5-20% of heat-conducting filler subjected to surface treatment and 1-20% of flame retardant in percentage by mass; the heat-conducting filler is selected from heat-conducting fillers with the particle size of 0.5-50 mu m; preferably, the heat-conducting filler is selected from heat-conducting fillers with the particle size of 1-30 μm; more preferably, the heat conductive filler is formed by mixing a small-particle-diameter heat conductive filler having a particle diameter of 1 to 20 μm and a large-particle-diameter heat conductive filler having a particle diameter of 15 to 30 μm.
Particularly, the difference between the particle size of the large-particle-size heat-conducting filler and the particle size of the small-particle-size heat-conducting filler is at least more than 5-10 μm, preferably at least more than 8-15 μm, and more preferably at least more than 12-25 μm; and/or the mass ratio of the small-particle-size heat-conducting filler to the large-particle-size heat-conducting filler is 1: (2-8), preferably 1: (3-6).
In particular, the two-component potting silica gel comprises a component A and a component B, wherein the component A comprises vinyl silicone oil and a platinum catalyst, and the component B comprises vinyl silicone oil and hydrogen-containing silicone oil; the vinyl silicone oil is selected from the group consisting of terminal vinyl silicone oil and side vinyl silicone oil; the number of vinyl contained in the vinyl silicone oil is not less than 2; the phase change microcapsule has a phase change temperature of 20-80 ℃ and phase change latent heat of 150-220 kJ/kg; the phase-change microcapsule accounts for 7-20% of the heat-conducting heat-storing multifunctional encapsulating silica gel by mass, and preferably accounts for 7-15%; the thermally conductive filler is selected from the group consisting of zinc oxide, aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and silicon carbide; preferably, the thermally conductive filler is selected from the group consisting of aluminum oxide, aluminum nitride, and silicon carbide; more preferably, the thermally conductive filler is selected from the group consisting of aluminum oxide and aluminum nitride; the heat-conducting filler accounts for 7-20% of the heat-conducting heat-storing multifunctional encapsulating silica gel by mass, and is preferably 7-15%; and/or the flame retardant is selected from the group consisting of decabromodiphenyl ether, ammonium polyphosphate, silicone flame retardant, ammonium polyphosphate and montmorillonite nanocomposite, terpene resin, magnesium hydroxide, antimony trioxide and aluminum hydroxide; preferably, the flame retardant is selected from the group consisting of decabromodiphenyl ether, terpene resin and antimony trioxide; more preferably, the flame retardant consists of decabromodiphenyl ether, a terpene resin and antimony trioxide, and the mass ratio of decabromodiphenyl ether: terpene resin: the mass ratio of the antimony trioxide is 3:1: 1; the flame retardant accounts for 5-20% by mass of the heat-conducting heat-storing multifunctional encapsulating silica gel, and preferably accounts for 5-10% by mass of the heat-conducting heat-storing multifunctional encapsulating silica gel.
In particular, the vinyl silicone oil is selected from vinyl silicone oils having a viscosity of from 100 mPas to 1500 mPas; preferably, the vinyl silicone oil is selected from vinyl silicone oil with viscosity of 100 mPas-800 mPas; more preferably, the vinyl silicone oil is prepared by mixing low-viscosity vinyl silicone oil with the viscosity of 100 to 500 mPas and high-viscosity vinyl silicone oil with the viscosity of 400 to 800 mPas; the difference value of the viscosity of the high-viscosity vinyl silicone oil and the viscosity of the low-viscosity vinyl silicone oil is at least more than 200 mPas-300 mPas, preferably at least more than 300 mPas-400 mPas, and more preferably at least more than 500 mPas-600 mPas; and/or the mass ratio of the low-viscosity vinyl silicone oil to the high-viscosity vinyl silicone oil is 1: (1 to 10), preferably 1: (4-8).
Particularly, the coupling agent used for the surface treatment of the heat-conducting filler is a silane coupling agent; the silane coupling agent is selected from the group consisting of methyltriethoxysilane, n-propyltriethoxysilane, n-octyltriethoxysilane, and vinyltriethoxysilane; preferably, the silane coupling agent is selected from the group consisting of n-octyltriethoxysilane and vinyltriethoxysilane; more preferably, the silane coupling agent is n-octyltriethoxysilane.
The invention provides a preparation method of heat-conducting heat-storing multifunctional encapsulating silica gel in a second aspect, which comprises the following steps:
(1) surface treatment of the heat-conducting filler: uniformly mixing a silane coupling agent, water and ethanol to obtain a hydrolyzed silane coupling agent, then carrying out surface treatment on heat-conducting fillers with different particle sizes by using the hydrolyzed silane coupling agent under the water bath condition of 50-70 ℃ to obtain a heat-conducting filler mixed solution with the treated surface, carrying out solid-liquid separation on the heat-conducting filler mixed solution with the treated surface through centrifugation to separate out solid substances of the heat-conducting filler, and drying the solid substances of the heat-conducting filler to obtain the heat-conducting fillers with the treated surfaces with different particle sizes;
(2) preparing a heat-conducting heat-storing composite filler: uniformly mixing the surface-treated heat-conducting filler with different particle sizes prepared in the step (1) with the phase-change microcapsules to prepare a heat-conducting heat-storing composite filler;
(3) preparation of A component and B component in the two-component encapsulating silica gel: uniformly mixing vinyl silicone oil with different viscosities with a platinum catalyst and foaming the mixture side by side to prepare a component A; uniformly mixing vinyl silicone oil with different viscosities with hydrogen-containing silicone oil and foaming to prepare a component B;
(4) preparation of A1 component and B1 component in the heat-conducting heat-storage multifunctional encapsulating silica gel: uniformly mixing the component A prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component A1; uniformly mixing the component B prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component B1; and
(5) preparing heat-conducting and heat-storing multifunctional encapsulating silica gel: and (3) uniformly mixing the A1 component, the B1 component and the flame retardant prepared in the step (4), and then sequentially carrying out bubble discharge and curing molding to prepare the heat-conducting heat-storing multifunctional encapsulating silica gel.
Preferably, the platinum catalyst in step (3) is a platinum-vinylsiloxane complex; the method further comprises, prior to step (3), preparing a platinum-vinylsiloxane complex: mixing 1, 3-tetramethyl divinyl disiloxane and chloroplatinic acid to obtain a mixed solution, refluxing the mixed solution for 1-1.5 hours under the condition that nitrogen is introduced and the temperature of the mixed solution is 100-120 ℃ to obtain a platinum-vinyl siloxane complex pre-product, and sequentially performing a step of centrifuging the platinum-vinyl siloxane complex pre-product to remove platinum black, a step of washing the platinum-vinyl siloxane complex pre-product with water until the pH value of the platinum-vinyl siloxane complex pre-product is 6.8-7.3 and a step of drying to obtain the platinum-vinyl siloxane complex.
Preferably, the mass ratio of the silane coupling agent, water and ethanol in the step (1) is 1: (3-5): (100-200); in the step (1), the amount of the silane coupling agent accounts for 1-3% of the amount of the heat-conducting filler by mass percent; the amount of the platinum catalyst in the component A prepared in the step (3) accounts for 1-10% of the amount of the vinyl silicone oil by mass percent; the amount of the hydrogen-containing silicone oil in the component B prepared in the step (3) accounts for 1-10% of the amount of the vinyl silicone oil by mass percent; and/or the mass percentage of the component A1 to the component B1 in the step (5) is 1: 1.
Preferably, the speed of the centrifugation in the step (1) is 1200-1600 r/min, and the time of the centrifugation is 5-8 min; the drying in the step (1) is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 10-14 h; the bubble removal in the step (3), the step (4) and the step (5) is carried out under the vacuum condition; and/or the curing molding in the step (5) is carried out at room temperature or under heating.
Preferably, in the preparation of the platinum-vinylsiloxane complex, the solution used for the water washing is a sodium bicarbonate solution, preferably having a concentration of between 2% and 4% by weight; in the preparation of the platinum-vinylsiloxane complex, the drying agent used for the drying was calcium chloride.
Compared with the prior art, the invention at least has the following beneficial effects:
1. according to the invention, the vinyl silicone oils with different high and low viscosities are mixed and compounded for use, so that not only is the viscosity of the silica gel system reduced, but also more vinyl groups are introduced through the low-viscosity vinyl silicone oil, so that the number of crosslinking points in the system is increased, and the mechanical property of the silica gel is improved.
2. According to the invention, the surface treatment is carried out on the heat-conducting filler, so that the uniform dispersibility of the heat-conducting filler in the silica gel matrix is increased, the viscosity of the heat-conducting heat-storing multifunctional encapsulating silica gel is greatly reduced under the condition that the addition amount of the heat-conducting filler is the same, or the addition amount of the heat-conducting filler is increased under the condition that the viscosity of the silica gel is not changed, so that the heat-conducting property of the heat-conducting heat-storing multifunctional encapsulating silica gel is.
3. According to the invention, the heat-conducting fillers with different particle sizes are mixed and filled for use, so that a close packing effect is achieved, contact points in the system are increased, and a heat-conducting network chain in the system is easier to form. The heat conduction performance of the heat conduction and heat storage multifunctional encapsulating silica gel is further improved under the condition that the heat conduction performance of the encapsulating silica gel system is not reduced and the system viscosity is greatly reduced or the silica gel viscosity is unchanged.
4. By adding the phase-change microcapsule, the invention avoids the serious problems of melt flow, infiltration migration and graphite electric conduction of the traditional paraffin/graphite composite phase-change material during phase change, and ensures that the heat-conducting and heat-storing multifunctional encapsulating silica gel has good heat-storing and temperature-controlling performances.
5. The heat-conducting heat-storing multifunctional encapsulating silica gel contains the phase-change microcapsules, can regulate and control the temperature of a battery pack, an electronic component and the like, enables the battery pack to operate in an optimal working temperature range, and improves the overall efficiency of equipment.
6. The heat-conducting and heat-storing multifunctional encapsulating silica gel disclosed by the invention contains a high-efficiency flame retardant, so that the combustion problem of a battery pack caused by accidents can be effectively prevented, and the safety performance of the battery pack is greatly improved.
7. The heat-conducting heat-storing multifunctional encapsulating silica gel has good heat-conducting property and heat-storing temperature-controlling property, can be used for the heat management of battery packs of high-power electronic components, high-density integrated circuits, solar panels, new energy automobile power lithium batteries and other batteries, and can effectively absorb heat and quickly conduct and diffuse when the heating power of the electronic components is overlarge and the single batteries in the battery packs are overheated, so that the temperature uniformity among the single batteries in the battery packs is ensured.
Drawings
Fig. 1 is a schematic structural view of a thermally conductive filler of the same particle size.
Fig. 2 is a schematic structural view of a mixture of a small-particle-size heat-conductive filler and a large-particle-size heat-conductive filler.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few 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.
The invention provides a heat-conducting heat-storing multifunctional encapsulating silica gel in a first aspect, wherein the heat-conducting heat-storing multifunctional encapsulating silica gel consists of 40-89% (such as 40%, 50%, 60%, 70%, 80%, 85% or 89%) of two-component encapsulating silica gel, 5-20% (such as 5%, 10%, 13%, 15%, 18% or 20%) of phase-change microcapsules, 5-20% (such as 5%, 7%, 10%, 13%, 15% or 20%) of surface-treated heat-conducting filler and 1-20% (such as 1%, 2%, 5%, 10%, 15% or 20%) of flame retardant in percentage by mass; the heat-conducting filler is selected from heat-conducting fillers with the particle size of 0.5-50 μm (such as 0.5, 1, 5, 10, 15, 20, 40 or 50 μm); preferably, the thermally conductive filler is selected from thermally conductive fillers having a particle size of 1 μm to 30 μm (e.g., 1, 5, 10, 15, 20, or 30 μm); more preferably, the heat conductive filler is formed by mixing a small-particle-size heat conductive filler having a particle size of 1 to 20 μm (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 μm) and a large-particle-size heat conductive filler having a particle size of 15 to 30 μm (e.g., 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 μm).
According to some preferred embodiments, the difference in particle size between the large-particle size thermally conductive filler and the small-particle size thermally conductive filler is at least greater than 5 μm to 10 μm (e.g., 5, 6, 7, 8, 9, or 10 μm), preferably at least greater than 8 μm to 15 μm (e.g., 8, 9, 10, 11, 12, 13, 14, or 15 μm), and more preferably at least greater than 12 μm to 25 μm (e.g., 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25 μm). Specifically, for example, a small-particle-diameter heat conductive filler of 5 μm is mixed with a large-particle-diameter heat conductive filler of 30 μm, a small-particle-diameter heat conductive filler of 10 μm is mixed with a large-particle-diameter heat conductive filler of 30 μm, or a small-particle-diameter heat conductive filler of 15 μm is mixed with a large-particle-diameter heat conductive filler of 30 μm.
The heat-conducting filler is formed by mixing and filling a large-particle-size heat-conducting filler and a small-particle-size heat-conducting filler according to a certain proportion, and the small-particle-size heat-conducting filler can be better filled into gaps among the large-particle-size heat-conducting fillers, so that contact points in a system are increased, a heat-conducting network chain in the system is easier to form, the most effective compact stacking effect is achieved, the viscosity of a silica gel substrate is reduced as much as possible on the premise that the heat-conducting coefficient is not reduced, or the heat-conducting performance of the heat-conducting heat-storing multifunctional encapsulating silica gel is further improved under the condition that the viscosity of the silica gel is not. The structural schematic diagram of the mixed small-particle-size heat-conducting filler and large-particle-size heat-conducting filler is shown in fig. 2, and the small-particle-size heat-conducting filler is filled in the gap between the large-particle-size heat-conducting fillers.
According to some preferred embodiments, the mass ratio of the small-particle-size heat-conductive filler to the large-particle-size heat-conductive filler is 1: (2-8) (e.g., 1:2, 1:4, 1:6, or 1:8), preferably 1: (3-6) (e.g., 1:3, 1:4, 1:5, or 1: 6).
The content of the two-component potting silica gel in the heat-conducting and heat-storing multifunctional potting silica gel is preferably 60% to 89% (e.g., 60%, 70%, 75%, 80%, 85% or 89%) by mass, and more preferably 70% to 85% (e.g., 70%, 75%, 80% or 85%). The two-component silicone potting gel of the present invention is not particularly limited, and may be, for example, a commercially available two-component silicone potting gel containing a component a and a component B.
According to some preferred embodiments, the two-component potting silicone comprises an a-component comprising a vinyl silicone oil and a platinum catalyst and a B-component comprising a vinyl silicone oil and a hydrogen-containing silicone oil; the vinyl silicone oil is selected from the group consisting of terminal vinyl silicone oil and side vinyl silicone oil; the vinyl silicone oil contains vinyl groups with the number not less than 2, and the vinyl groups can be used for bonding reaction with silicon.
According to some preferred embodiments, the vinyl silicone oil is selected from vinyl silicone oils having a viscosity of from 100 to 1500 mPa-s (e.g. 100, 200, 300, 400, 500, 600, 700, 800, 1000, 1200 or 1500 mPa-s); preferably, the vinyl silicone oil is selected from vinyl silicone oils having a viscosity of 100 to 800mPa · s (e.g., 100, 200, 300, 400, 500, 600, 700, or 800mPa · s); more preferably, the vinyl silicone oil is prepared by mixing a low viscosity vinyl silicone oil having a viscosity of 100 to 500 mPas (for example, 100, 200, 300, 400 or 500 mPas) and a high viscosity vinyl silicone oil having a viscosity of 400 to 800 mPas (for example, 400, 500, 600, 700 or 800 mPas); the difference between the viscosity of the high-viscosity vinyl silicone oil and the viscosity of the low-viscosity vinyl silicone oil is at least more than 200 mPas to 300 mPas (such as 200 or 300 mPas), preferably at least more than 300 mPas to 400 mPas (such as 300 or 400 mPas), and more preferably at least more than 500 mPas to 600 mPas (such as 500 or 600 mPas). Specifically, for example, a vinyl silicone oil having a viscosity of 200 mPas is mixed with a vinyl silicone oil having a viscosity of 800 mPas, a vinyl silicone oil having a viscosity of 200 mPas is mixed with a vinyl silicone oil having a viscosity of 700 mPas, a vinyl silicone oil having a viscosity of 100 mPas is mixed with a vinyl silicone oil having a viscosity of 700 mPas, or a vinyl silicone oil having a viscosity of 200 mPas is mixed with a vinyl silicone oil having a viscosity of 600 mPas.
According to some preferred embodiments, the mass ratio of the low-viscosity vinyl silicone oil to the high-viscosity vinyl silicone oil is 1: (1-10) (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, or 1:10), preferably 1: (4-8) (e.g., 1:4, 1:5, 1:6, 1:7, or 1: 8). In the invention, two vinyl silicone oils with different viscosities (high-viscosity vinyl silicone oil and low-viscosity vinyl silicone oil) are mixed and compounded for use, which is beneficial to reducing the viscosity of a system, can increase the addition of the phase-change microcapsules and further improve the heat storage function of the heat-conducting heat-storage multifunctional encapsulating silica gel.
According to some preferred embodiments, the phase-change microcapsules are phase-change microcapsules having a phase-change temperature of 20 ℃ to 80 ℃ (e.g., 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃) and a latent heat of phase change of 150 to 220kJ/kg (e.g., 150, 160, 170, 180, 190, 200, 210 or 220 kJ/kg); the content of the phase-change microcapsules in the heat-conducting heat-storing multifunctional encapsulating silica gel is 7-20% (e.g. 7%, 8%, 9%, 10%, 12%, 13%, 15%, 18% or 20%) by mass, preferably 7-15% (e.g. 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%).
The phase-change microcapsule can be a commercially available phase-change microcapsule, for example, a low-temperature thermal-control phase-change microcapsule which takes paraffin as a core material, takes urea resin as a shell and also contains a heat-conducting filler, wherein the heat-conducting filler is added in the process of coating paraffin by urea resin, and the addition amount of the heat-conducting filler is 5-30% of the mass percent of paraffin. The specific preparation method of the low-temperature thermal control phase change microcapsule can comprise the following steps: firstly, paraffin preheating treatment; secondly, synthesizing a urea resin prepolymer; thirdly, carrying out polymerization reaction on the styrene maleic anhydride resin solution, water and inorganic salt; fourthly, mixing the materials to obtain a mixture; fifthly, shearing and emulsifying the mixture to obtain solid-liquid phase change prepolymer mixed emulsion; sixthly, dropwise adding acid into the solid-liquid phase change prepolymer mixed emulsion, starting a coating reaction, and adjusting the pH value to 5-6; seventhly, after the coating reaction is carried out for 1-2 hours, adding a heat-conducting filler into the mixed emulsion, uniformly stirring, dropwise adding acid, adjusting the pH value to 3-4, and continuing until the coating reaction is finished; and eighthly, obtaining the low-temperature thermal control phase change microcapsule after suction filtration and drying.
According to some preferred embodiments, the thermally conductive filler is selected from the group consisting of zinc oxide, aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and silicon carbide; preferably, the thermally conductive filler is selected from the group consisting of aluminum oxide, aluminum nitride, and silicon carbide; more preferably, the thermally conductive filler is selected from the group consisting of aluminum oxide and aluminum nitride; the heat-conducting filler accounts for 7-20% (e.g. 7%, 8%, 9%, 10%, 12%, 13%, 15%, 18% or 20%) of the heat-conducting heat-storing multifunctional potting silica gel, and preferably accounts for 7-15% (e.g. 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%).
According to some preferred embodiments, the flame retardant is selected from the group consisting of decabromodiphenyl ether, ammonium polyphosphate, silicone flame retardants, ammonium polyphosphate and montmorillonite nanocomposites, terpene resins, magnesium hydroxide, antimony trioxide and aluminum hydroxide; preferably, the flame retardant is selected from the group consisting of decabromodiphenyl ether, terpene resin and antimony trioxide; more preferably, the flame retardant consists of decabromodiphenyl ether, a terpene resin and antimony trioxide, and the mass ratio of decabromodiphenyl ether: terpene resin: the mass ratio of antimony trioxide is 3:1:1, and the flame retardant can obtain a better flame retardant effect at the mass ratio; the flame retardant accounts for 5-20% (e.g. 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%) of the heat-conducting heat-storing multifunctional potting silica gel, preferably 5-10% (e.g. 5%, 6%, 7%, 8%, 9% or 10%).
According to some preferred embodiments, the coupling agent used for the surface treatment of the thermally conductive filler is a silane coupling agent; the silane coupling agent is selected from the group consisting of methyltriethoxysilane, n-propyltriethoxysilane, n-octyltriethoxysilane, and vinyltriethoxysilane; preferably, the silane coupling agent is selected from the group consisting of n-octyltriethoxysilane and vinyltriethoxysilane; more preferably, the silane coupling agent is n-octyltriethoxysilane.
According to some more preferred embodiments, the heat-conducting potting silica gel consists of, by mass, 70% to 80% of a two-component potting silica gel, 7% to 15% of a surface-treated heat-conducting filler, 7% to 15% of a phase-change microcapsule, and 5% to 10% of a flame retardant. The heat-conducting encapsulating silica gel in mass ratio has the advantages of high heat conductivity, good temperature control capability, good flame retardant property, good heat dissipation, water resistance, shock resistance and strong aging resistance.
The invention provides a preparation method of heat-conducting heat-storing multifunctional encapsulating silica gel in a second aspect, which comprises the following steps:
(1) surface treatment of the heat-conducting filler: uniformly mixing a silane coupling agent, water and ethanol to obtain a hydrolyzed silane coupling agent, then carrying out surface treatment on heat-conducting fillers with different particle sizes by using the hydrolyzed silane coupling agent under the water bath condition of 50-70 ℃ (such as 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃) to obtain a heat-conducting filler mixed solution with the treated surface, carrying out solid-liquid separation on the heat-conducting filler mixed solution with the treated surface by centrifugation to separate out solid matters of the heat-conducting filler, and drying the solid matters of the heat-conducting filler to obtain the heat-conducting fillers with the treated surface with different particle sizes; the amount of the silane coupling agent is 1 to 3 mass percent (e.g., 1, 2, or 3 mass percent) of the amount of the heat conductive filler.
(2) Preparing a heat-conducting heat-storing composite filler: uniformly mixing the surface-treated heat-conducting filler with different particle sizes prepared in the step (1) with phase-change microcapsules according to a certain proportion to prepare a heat-conducting heat-storing composite filler;
(3) preparation of A component and B component in the two-component encapsulating silica gel: uniformly mixing vinyl silicone oil with different viscosities with a platinum catalyst and foaming the mixture side by side to prepare a component A; uniformly mixing vinyl silicone oil with different viscosities with hydrogen-containing silicone oil and foaming to prepare a component B;
(4) preparation of A1 component and B1 component in the heat-conducting heat-storage multifunctional encapsulating silica gel: uniformly mixing the component A prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component A1; uniformly mixing the component B prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component B1; and
(5) preparing heat-conducting and heat-storing multifunctional encapsulating silica gel: uniformly mixing the A1 component, the B1 component and the flame retardant prepared in the step (4), and then sequentially carrying out bubble discharge and curing molding to prepare the heat-conducting heat-storing multifunctional encapsulating silica gel; for example, the mass percentage of the A1 component to the B1 component is preferably 1: 1.
Particularly, the preparation of the A1 component and the B1 component in the heat-conducting heat-storing encapsulating silica gel can also be prepared by the following steps:
uniformly mixing vinyl silicone oil with different viscosities, a platinum catalyst and the heat-conducting heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare an A1 component; and (3) uniformly mixing vinyl silicone oil with different viscosities, hydrogen-containing silicone oil and the heat-conducting heat-storing composite filler prepared in the step (2) and foaming to prepare a component B1.
According to some preferred embodiments, the amount of the platinum catalyst is 1% to 10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%) by mass based on the amount of the vinyl silicone oil of the a1 component; the amount of the hydrogen-containing silicone oil accounts for 1-10% by mass (for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%) of the amount of the vinyl silicone oil of the component B1.
According to some preferred embodiments, the platinum catalyst is a platinum-vinylsiloxane complex; the method further comprises, prior to step (3), preparing a platinum-vinylsiloxane complex: mixing 1, 3-tetramethyldivinyldisiloxane and chloroplatinic acid to obtain a mixed solution, refluxing the mixed solution for 1 to 1.5 hours (for example, 1 hour or 1.5 hours) at the temperature of 100 ℃ to 120 ℃ (for example, 100 ℃, 110 ℃ or 120 ℃) by introducing nitrogen and the mixed solution to obtain a platinum-vinylsiloxane complex pre-product, and sequentially performing a step of centrifuging the platinum-vinylsiloxane complex pre-product to remove platinum black, a step of washing the platinum-vinylsiloxane complex pre-product with water until the pH of the platinum-vinylsiloxane complex pre-product is 6.8 to 7.3 (for example, 6.8, 6.9, 7.0, 7.1, 7.2 or 7.3) and a step of drying to obtain the platinum-vinylsiloxane complex.
According to some preferred embodiments, the mass ratio of the silane coupling agent, water and ethanol in step (1) is 1: (3-5): (100-200), for example 1:3:100, 1:4:150 or 1:5: 200; the centrifugation speed in the step (1) is 1200-1600 r/min (such as 1200, 1300, 1400, 1500 or 1600r/min), and the centrifugation time is 5-8 min (such as 5, 6, 7 or 8 min); the drying in the step (1) is vacuum drying, the drying temperature is 70-80 ℃ (such as 70 ℃, 75 ℃ or 80 ℃), and the drying time is 10-14 h (such as 10, 11, 12, 13 or 14 h); the bubble removal in the steps (3) and (4) is carried out under vacuum conditions; the curing molding in the step (4) is performed at room temperature or under a heating condition.
According to some preferred embodiments, in the preparation of the platinum-vinylsiloxane complex, the solution used for the water wash is a sodium bicarbonate solution, preferably having a concentration of 2% to 4% by weight (for example 2%, 3% or 4%); in the preparation of the platinum-vinylsiloxane complex, the drying agent used for the drying was calcium chloride.
The heat-conducting heat-storing multifunctional encapsulating silica gel disclosed by the invention is tested for viscosity according to GB/T2794; testing thermal conductivity according to ASTM D5470; testing the density according to GB/T2008; testing the hardness according to GB/T531.1-2008; GB/T528-; testing the volume resistivity according to GB/T1692-2008; testing the breakdown voltage strength according to GB/T1695; the flame retardant rating was tested according to UL 94.
Example 1
Firstly, uniformly mixing nano alumina powder with the particle sizes of 15 microns and 30 microns according to the mass ratio of 1:4, then respectively weighing 14g of uniformly mixed heat-conducting filler and 0.14g of n-octyltriethoxysilane serving as a silane coupling agent, preparing the n-octyltriethoxysilane and water into a solution according to the molar ratio of 1:3, adding a proper amount of ethanol, uniformly mixing, and standing for 20 min. And slowly adding the hydrolyzed silane coupling agent solution into the heat-conducting filler, fully stirring until the silane coupling agent solution is uniformly dispersed, and heating and stirring the mixed solution under the condition of 65 ℃ water bath to enable the hydrolyzed silane coupling agent to carry out surface treatment on the heat-conducting filler, thereby obtaining the heat-conducting filler mixed solution with the surface treated. And centrifuging the mixed liquid of the heat-conducting filler after surface treatment for 6min at the centrifugation speed of 1500r/min to perform solid-liquid separation and separate out solid matters of the heat-conducting filler, putting the solid matters of the heat-conducting filler into a 75 ℃ drying box for vacuum drying treatment for 13.5h, and drying to obtain the heat-conducting filler after surface treatment.
And secondly, adding 16g of phase change microcapsules into the heat conduction filler obtained in the step I, and stirring to uniformly mix the phase change microcapsules to obtain the heat conduction and heat storage composite filler. The phase change temperature of the phase change microcapsule is 48 ℃, and the phase change latent heat is 185 kJ/kg.
③ weighing 50g of 1, 3-tetramethyl divinyl disiloxane and 2g of chloroplatinic acid, mixing in a three-neck flask to obtain a mixed solution, keeping the mixed solution under the condition of introducing nitrogen and stirring and refluxing for 1h at the temperature of 100 ℃ to obtain a platinum-vinyl siloxane complex pre-product, cooling the platinum-vinyl siloxane complex pre-product, sequentially centrifuging to remove platinum black, and using NaHCO3The solution was washed to pH 7 and then with CaCl2Drying to obtain the platinum-vinyl siloxane complex.
Respectively weighing vinyl-terminated silicone oil with the viscosity of 100mPa & s and 700mPa & s, uniformly mixing according to the mass ratio of 1:8, weighing 3g of the catalyst prepared in the step three, adding the catalyst into 100g of the uniformly mixed vinyl silicone oil, mixing the mixture under a high-speed shearing machine at the rotating speed of 20r/min, fully and uniformly mixing, and vacuumizing and exhausting bubbles to obtain a component A; weighing 3g of hydrogen-containing silicone oil, adding into 100g of uniformly mixed vinyl silicone oil, mixing under a high-speed shearing machine at a rotating speed of 20r/min, fully and uniformly mixing, and vacuumizing and discharging bubbles to obtain the component B. Respectively weighing 30gA and 30gB components for later use.
Adding 15g of the heat-conducting and heat-storing composite filler prepared in the step II into 30g of the component A, fully stirring and uniformly mixing the mixture, and vacuumizing the mixture to discharge bubbles to obtain a component A1; and (3) adding 15g of the heat-conducting and heat-storing composite filler prepared in the step (II) into 30g of the component B, fully stirring and uniformly mixing, and vacuumizing to discharge bubbles to obtain the component B1.
Sixthly, adding 10g of flame retardant into the components A1 and B1 prepared in the fifth step, stirring and mixing uniformly, placing the mixture in vacuum bubble discharge equipment, vacuumizing and discharging bubbles for about 10min, maintaining the vacuum degree for about 5min, and curing and forming at room temperature or under a heating condition to prepare the heat conduction and heat storage multifunctional encapsulating silica gel based on the phase change microcapsule; the flame retardant is prepared from decabromodiphenyl ether, antimony trioxide and terpene resin according to the mass ratio of 3:1: 1.
The detection results of viscosity, thermal conductivity, density, hardness, tensile strength, volume resistivity, breakdown voltage strength and flame retardant rating of the heat-conducting heat-storing multifunctional encapsulating silica gel in example 1 are shown in table 1.
Example 2
Firstly, uniformly mixing 15 mu m and 30 mu m nanometer alumina powder according to a mass ratio of 1/4, then respectively weighing 14g of uniformly mixed heat-conducting filler and 0.14g of n-octyltriethoxysilane as a silane coupling agent, preparing the n-octyltriethoxysilane and water into a solution according to a molar ratio of 1:3, adding a proper amount of ethanol, uniformly mixing, and standing for 20 min. And slowly adding the hydrolyzed silane coupling agent solution into the heat-conducting filler, fully stirring until the silane coupling agent solution is uniformly dispersed, and heating and stirring the mixed solution under the condition of 65 ℃ water bath to enable the hydrolyzed silane coupling agent to carry out surface treatment on the heat-conducting filler, thereby obtaining the heat-conducting filler mixed solution with the surface treated. And centrifuging the mixed liquid of the heat-conducting filler after surface treatment for 6min at the centrifugation speed of 1500r/min to perform solid-liquid separation and separate out solid matters of the heat-conducting filler, putting the solid matters of the heat-conducting filler into a 75 ℃ drying box for vacuum drying treatment for 13.5h, and drying to obtain the heat-conducting filler after surface treatment.
And secondly, adding 16g of phase change microcapsules into the heat conduction filler obtained in the step I, and stirring to uniformly mix the phase change microcapsules to obtain the heat conduction and heat storage composite filler. The phase change temperature of the phase change microcapsule is 48 ℃, and the phase change latent heat is 185 kJ/kg.
③ weighing 50g of 1, 3-tetramethyl divinyl disiloxane and 2g of chloroplatinic acid, mixing in a three-neck flask to obtain a mixed solution, keeping the mixed solution under the condition of introducing nitrogen and stirring and refluxing for 1h at the temperature of 100 ℃ to obtain a platinum-vinyl siloxane complex pre-product, cooling the platinum-vinyl siloxane complex pre-product, sequentially centrifuging to remove platinum black, and using NaHCO3The solution was washed to pH 7 and then with CaCl2Drying to obtain the platinum-vinyl siloxane complex.
Weighing 3g of the catalyst prepared in the step (III), adding the catalyst into 100g of vinyl silicone oil with the same viscosity, mixing the catalyst and the vinyl silicone oil under a high-speed shearing machine at the rotating speed of 20r/min, fully and uniformly mixing the catalyst and the vinyl silicone oil, and vacuumizing and discharging bubbles to obtain a component A; weighing 3g of hydrogen-containing silicone oil, adding into 100g of uniformly mixed vinyl silicone oil, mixing under a high-speed shearing machine at a rotating speed of 20r/min, fully and uniformly mixing, and vacuumizing and discharging bubbles to obtain the component B. Respectively weighing 30gA and 30gB components for later use.
Adding 15g of the heat-conducting and heat-storing composite filler prepared in the step II into 30g of the component A, fully stirring and uniformly mixing the mixture, and vacuumizing the mixture to discharge bubbles to obtain a component A1; and (3) adding 15g of the heat-conducting and heat-storing composite filler prepared in the step (II) into 30g of the component B, fully stirring and uniformly mixing, and vacuumizing to discharge bubbles to obtain the component B1.
Sixthly, adding 10g of flame retardant into the components A1 and B1 prepared in the fifth step, stirring and mixing uniformly, placing the mixture in vacuum bubble discharge equipment, vacuumizing and discharging bubbles for about 10min, maintaining the vacuum degree for about 5min, and curing and forming at room temperature or under a heating condition to prepare the heat conduction and heat storage multifunctional encapsulating silica gel based on the phase change microcapsule; the flame retardant is prepared from decabromodiphenyl ether, antimony trioxide and terpene resin according to the mass ratio of 3:1: 1.
The detection results of viscosity, thermal conductivity, density, hardness, tensile strength, volume resistivity, breakdown voltage strength and flame retardant rating of the heat-conducting heat-storing multifunctional encapsulating silica gel in example 2 are shown in table 1.
Examples 3-22 were conducted in substantially the same manner as in example 1 except as set forth in Table 1.
Specifically, C1 in table 1 indicates that the a component and the terminal vinyl silicone oil of which vinyl silicone oil in the B component has a viscosity of 100mPa · s and 700mPa · s are mixed in a mass ratio of 1: 8; c2 represents that the vinyl silicone oil in the component A and the vinyl silicone oil in the component B are terminal vinyl silicone oil with the same viscosity; c3 represents that the vinyl silicone oil in the component A and the vinyl silicone oil in the component B are mixed according to the mass ratio of 1:8, wherein the vinyl silicone oil is 200mPa & s and the terminal vinyl silicone oil has the viscosity of 800mPa & s; c4 represents that the vinyl silicone oil in the component A and the vinyl silicone oil in the component B are 100mPa & s and terminal vinyl silicone oil with the viscosity of 700mPa & s are mixed according to the mass ratio of 1: 6; c5 represents that the vinyl silicone oil in the component A and the vinyl silicone oil in the component B are mixed according to the mass ratio of 1:8, wherein the vinyl silicone oil is 400mPa & s and the vinyl silicone oil is terminal vinyl silicone oil with the viscosity of 600mPa & s; e1 represents a phase change microcapsule with a phase change temperature of 48 ℃; e2 represents a phase change microcapsule with a phase change temperature of 35 ℃; f1 shows that the nano-alumina heat-conducting filler with the grain diameter of 15 mu m and 30 mu m and surface treatment is mixed according to the mass ratio of 1: 4; f2 represents nano-alumina heat-conducting filler with the same particle size and subjected to surface treatment; f3 shows that the nano-alumina heat-conducting filler with the grain diameter of 10 mu m and 30 mu m and the surface treatment is mixed according to the mass ratio of 1: 4; f4 shows that the nano-alumina heat-conducting filler with the grain diameter of 15 mu m and 30 mu m and surface treatment is mixed according to the mass ratio of 1: 6; f5 represents nano alumina heat-conducting filler with the same particle size and without surface treatment; f6 shows that the nano-alumina heat-conducting filler with the grain diameter of 18 mu m and 23 mu m and the surface treatment is mixed according to the mass ratio of 1: 4; g represents a flame retardant prepared from decabromodiphenyl ether, antimony trioxide and terpene resin according to the mass ratio of 3:1: 1.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill 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 (18)
1. The utility model provides a multi-functional embedment silica gel of heat conduction heat-retaining which characterized in that:
the heat-conducting heat-storing multifunctional encapsulating silica gel consists of 40-89% of bi-component encapsulating silica gel, 5-20% of phase change microcapsule, 5-20% of surface-treated heat-conducting filler and 1-20% of flame retardant in percentage by mass; the flame retardant consists of decabromodiphenyl ether, terpene resin and antimony trioxide, and the mass ratio of the decabromodiphenyl ether: terpene resin: the mass ratio of the antimony trioxide is 3:1: 1; the heat-conducting filler is formed by mixing a small-particle-size heat-conducting filler with the particle size of 1-20 mu m and a large-particle-size heat-conducting filler with the particle size of 15-30 mu m;
the coupling agent used for the surface treatment of the heat-conducting filler is a silane coupling agent;
the surface treatment of the heat-conducting filler is as follows: uniformly mixing a silane coupling agent, water and ethanol to obtain a hydrolyzed silane coupling agent, then carrying out surface treatment on heat-conducting fillers with different particle sizes by using the hydrolyzed silane coupling agent under the water bath condition of 50-70 ℃ to obtain a heat-conducting filler mixed solution with the treated surface, carrying out solid-liquid separation on the heat-conducting filler mixed solution with the treated surface through centrifugation to separate out solid substances of the heat-conducting filler, and drying the solid substances of the heat-conducting filler to obtain the heat-conducting fillers with the treated surfaces with different particle sizes; wherein the mass ratio of the silane coupling agent to the water to the ethanol is 1: (3-5): (100-200); the mass percentage of the silane coupling agent in the heat-conducting filler is 1-3%;
the mass ratio of the small-particle-size heat-conducting filler to the large-particle-size heat-conducting filler is 1: (2-8);
the difference value of the particle sizes of the large-particle-size heat-conducting filler and the small-particle-size heat-conducting filler is more than 12 mu m;
the bicomponent encapsulating silica gel comprises a component A and a component B, wherein the component A comprises vinyl silicone oil and a platinum catalyst, and the component B comprises vinyl silicone oil and hydrogen-containing silicone oil; the vinyl silicone oil is selected from the group consisting of terminal vinyl silicone oil and side vinyl silicone oil;
the phase change microcapsule has a phase change temperature of 20-80 ℃ and phase change latent heat of 150-220 kJ/kg;
the vinyl silicone oil is formed by mixing low-viscosity vinyl silicone oil with the viscosity of 100-500 mPa.s and high-viscosity vinyl silicone oil with the viscosity of 400-800 mPa.s; the difference value of the viscosity of the high-viscosity vinyl silicone oil and the viscosity of the low-viscosity vinyl silicone oil is more than 500mPa & s; the mass ratio of the low-viscosity vinyl silicone oil to the high-viscosity vinyl silicone oil is 1: (1-10).
2. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 1, wherein:
the mass ratio of the small-particle-size heat-conducting filler to the large-particle-size heat-conducting filler is 1: (3-6).
3. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 1 or 2, wherein:
the number of vinyl contained in the vinyl silicone oil is not less than 2;
the phase change microcapsule accounts for 7-20% of the heat-conducting and heat-storing multifunctional encapsulating silica gel in percentage by mass;
the thermally conductive filler is selected from the group consisting of zinc oxide, aluminum oxide, magnesium oxide, aluminum nitride, boron nitride, and silicon carbide;
the heat-conducting filler accounts for 7-20% of the heat-conducting heat-storing multifunctional encapsulating silica gel in percentage by mass; and/or
The flame retardant accounts for 5-20% of the heat-conducting and heat-storing multifunctional encapsulating silica gel by mass.
4. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 3, wherein:
the phase change microcapsule accounts for 7-15% of the heat-conducting and heat-storing multifunctional encapsulating silica gel in percentage by mass.
5. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 3, wherein:
the thermally conductive filler is selected from the group consisting of aluminum oxide, aluminum nitride, and silicon carbide.
6. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 5, wherein:
the thermally conductive filler is selected from the group consisting of aluminum oxide and aluminum nitride.
7. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 3, wherein:
the heat-conducting filler accounts for 7-15% of the heat-conducting heat-storing multifunctional encapsulating silica gel in percentage by mass.
8. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 3, wherein:
the flame retardant accounts for 5-10% of the heat-conducting and heat-storing multifunctional encapsulating silica gel in percentage by mass.
9. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 1, wherein:
the mass ratio of the low-viscosity vinyl silicone oil to the high-viscosity vinyl silicone oil is 1: (4-8).
10. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 1, wherein:
the silane coupling agent is selected from the group consisting of methyltriethoxysilane, n-propyltriethoxysilane, n-octyltriethoxysilane, and vinyltriethoxysilane.
11. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 10, wherein:
the silane coupling agent is selected from the group consisting of n-octyltriethoxysilane and vinyltriethoxysilane.
12. The heat-conducting heat-storing multifunctional encapsulating silica gel as claimed in claim 11, wherein:
the silane coupling agent is n-octyl triethoxysilane.
13. A preparation method of heat-conducting heat-storing multifunctional encapsulating silica gel is characterized by comprising the following steps:
(1) surface treatment of the heat-conducting filler: uniformly mixing a silane coupling agent, water and ethanol to obtain a hydrolyzed silane coupling agent, then carrying out surface treatment on heat-conducting fillers with different particle sizes by using the hydrolyzed silane coupling agent under the water bath condition of 50-70 ℃ to obtain a heat-conducting filler mixed solution with the treated surface, carrying out solid-liquid separation on the heat-conducting filler mixed solution with the treated surface through centrifugation to separate out solid substances of the heat-conducting filler, and drying the solid substances of the heat-conducting filler to obtain the heat-conducting fillers with the treated surfaces with different particle sizes; wherein the mass ratio of the silane coupling agent to the water to the ethanol is 1: (3-5): (100-200); the mass percentage of the silane coupling agent in the heat-conducting filler is 1-3%;
(2) preparing a heat-conducting heat-storing composite filler: uniformly mixing the surface-treated heat-conducting filler with different particle sizes prepared in the step (1) with the phase-change microcapsules to prepare a heat-conducting heat-storing composite filler;
(3) preparation of A component and B component in the two-component encapsulating silica gel: uniformly mixing vinyl silicone oil with different viscosities with a platinum catalyst and foaming the mixture side by side to prepare a component A; uniformly mixing vinyl silicone oil with different viscosities with hydrogen-containing silicone oil and foaming to prepare a component B;
(4) preparation of A1 component and B1 component in the heat-conducting heat-storage multifunctional encapsulating silica gel: uniformly mixing the component A prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component A1; uniformly mixing the component B prepared in the step (3) with the heat-conducting and heat-storing composite filler prepared in the step (2) and foaming the mixture to prepare a component B1; and
(5) preparing heat-conducting and heat-storing multifunctional encapsulating silica gel: uniformly mixing the A1 component, the B1 component and the flame retardant prepared in the step (4), and then sequentially carrying out bubble discharge and curing molding to prepare the heat-conducting heat-storing multifunctional encapsulating silica gel; the flame retardant consists of decabromodiphenyl ether, terpene resin and antimony trioxide, and the mass ratio of the decabromodiphenyl ether: terpene resin: the mass ratio of the antimony trioxide is 3:1: 1.
14. The method of manufacturing according to claim 13, wherein:
the platinum catalyst in the step (3) is a platinum-vinylsiloxane complex;
the method further comprises, prior to step (3), preparing a platinum-vinylsiloxane complex: mixing 1, 3-tetramethyl divinyl disiloxane and chloroplatinic acid to obtain a mixed solution, refluxing the mixed solution for 1-1.5 hours under the condition that nitrogen is introduced and the temperature of the mixed solution is 100-120 ℃ to obtain a platinum-vinyl siloxane complex pre-product, and sequentially performing a step of centrifuging the platinum-vinyl siloxane complex pre-product to remove platinum black, a step of washing the platinum-vinyl siloxane complex pre-product with water until the pH value of the platinum-vinyl siloxane complex pre-product is 6.8-7.3 and a step of drying to obtain the platinum-vinyl siloxane complex.
15. The production method according to claim 13 or 14, characterized in that:
the mass percentage of the platinum catalyst in the component A prepared in the step (3) to the vinyl silicone oil is 1-10%;
the amount of the hydrogen-containing silicone oil in the component B prepared in the step (3) accounts for 1-10% of the amount of the vinyl silicone oil by mass percent; and/or
The mass percentage of the component A1 to the component B1 in the step (5) is 1: 1.
16. The method of manufacturing according to claim 13, wherein:
the centrifugation speed in the step (1) is 1200-1600 r/min, and the centrifugation time is 5-8 min;
the drying in the step (1) is vacuum drying, the drying temperature is 70-80 ℃, and the drying time is 10-14 h;
the bubble removal in the step (3), the step (4) and the step (5) is carried out under the vacuum condition; and/or
The curing molding in the step (5) is performed at room temperature or under heating.
17. The method of claim 14, wherein:
in the preparation of the platinum-vinylsiloxane complex, the solution used for the water wash was a sodium bicarbonate solution;
in the preparation of the platinum-vinylsiloxane complex, the drying agent used for the drying was calcium chloride.
18. The method of claim 17, wherein:
the concentration of the sodium bicarbonate solution is 2wt% -4 wt%.
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| CN109320212B (en) * | 2018-10-22 | 2021-07-13 | 全球能源互联网研究院有限公司 | Phase-change heat storage material, phase-change heat storage brick and preparation method thereof |
| CN109679142A (en) * | 2018-12-17 | 2019-04-26 | 南京工业大学 | A kind of preparation method of the compound heat filling of macromolecule |
| CN110317578A (en) * | 2019-07-03 | 2019-10-11 | 张立强 | Phase-change thermal storage silica gel, preparation method and applications |
| CN112705702A (en) * | 2020-12-07 | 2021-04-27 | 中国科学院深圳先进技术研究院 | Aluminum powder surface modification method |
| CN113174232A (en) * | 2021-04-23 | 2021-07-27 | 深圳市红叶杰科技有限公司 | Heat-conducting and heat-storing multifunctional encapsulating silica gel and preparation method thereof |
| CN115433539A (en) * | 2022-09-15 | 2022-12-06 | 矽时代材料科技股份有限公司 | Phase-change latent heat organic silicon pouring sealant and preparation method thereof |
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