Efficient heat-conducting environment-friendly flame-retardant polyurethane foaming encapsulating material for battery module and preparation method of efficient heat-conducting environment-friendly flame-retardant polyurethane foaming encapsulating material

Abstract

The invention relates to the technical field of pouring sealants, and particularly discloses a high-efficiency heat-conducting environment-friendly flame-retardant polyurethane foaming pouring sealant for a battery module and a preparation method of the high-efficiency heat-conducting environment-friendly flame-retardant polyurethane foaming pouring sealant. The encapsulating material is formed by mixing a component A and a component B, wherein the component A comprises aliphatic isocyanate and aromatic isocyanate; the component B comprises high-resilience polyether polyol, environment-friendly flame-retardant polyester polyol, a halogen-free flame retardant, a heat-conducting filler and modified polydimethylsiloxane; the halogen-free flame retardant is a ternary flame-retardant system composed of TCPP, TEP and organophosphate; the heat-conducting filler contains glass beads, hollow ceramic particles, boron nitride and aluminum oxide microspheres; the modified polydimethylsiloxane contains fluoroaniline and polyethylene glycol. The efficient heat-conducting environment-friendly flame-retardant polyurethane foaming potting material for the battery module has the advantage that the defect that the environment-friendly performance of the polyurethane foaming potting material is still insufficient during use can be overcome.

Description

Technical Field

[0001] The present invention relates to the technical field of potting adhesives, and more specifically, to a highly efficient, heat-conductive, environment-friendly, flame-retardant polyurethane foam potting material for battery modules and a preparation method thereof. Background Art

[0002] As electric vehicles develop more and more rapidly, the structure of batteries has also undergone major changes. More and more automobile manufacturers are using cylindrical batteries, such as Tesla, BMW, and Mercedes-Benz. Unlike China's BYD which uses blade batteries, blade batteries require the use of a large amount of thermally conductive adhesive and thermally conductive structural adhesive. For cylindrical batteries, polyurethane foam potting materials can play a good buffering role and protect the stability of large cylindrical batteries. At the same time, there are key technical requirements for polyurethane foam potting materials, that is, the fire protection standard must meet the UL94-V0 standard. In order to make the polyurethane foam potting material meet the fire protection standard, halogen flame retardants are usually added to the polyurethane foam potting material. However, halogen flame retardants are toxic and may be released into the environment during use, thereby polluting the air, water and soil, so it is not environmentally friendly. Summary of the invention

[0003] In order to improve the defect that the environmental performance of polyurethane foam potting materials is still insufficient during use, the present application provides a high-efficiency thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules and a preparation method thereof.

[0004] In the first aspect, the present application provides a highly efficient, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for a battery module, which adopts the following technical solution: A highly efficient, heat-conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules, comprising a mixture of component A and component B in a mass percentage of (0.5-1.5): (0.2-1.8): Component A includes the following raw materials in percentage by mass: 15%-40% aliphatic isocyanate, 1%-3% aromatic isocyanate; Component B includes the following raw materials in percentage by mass: 4%-6% high resilience polyether polyol, 2%-4% environmentally friendly flame retardant polyester polyol, 27%-37% halogen-free flame retardant, 20%-30% thermal conductive filler, and 5%-7% modified polydimethylsiloxane; The halogen-free flame retardant is a ternary flame retardant system consisting of TCPP, TEP and organic phosphate; The thermally conductive filler contains glass microspheres, hollow ceramic microparticles, boron nitride and alumina microspheres; The modified polydimethylsiloxane contains fluoroaniline and polyethylene glycol.

[0005] The halogen-free flame retardant of the ternary flame retardant system composed of TCPP, TEP and organic phosphate does not contain halogen, which improves the environmental friendliness of the potting material. When the potting material is subjected to high temperature, TCPP, TEP and organic phosphate will begin to decompose, releasing phosphoric acid and its derivatives, so that the potting material forms a dense elastic layer at high temperature, thereby blocking oxygen and isolating the fire source.

[0006] At the same time, glass microspheres and hollow ceramic particles are hollow structures, alumina microspheres have a porous structure, and the flaky structure of boron nitride can form a layered structure in the material. Therefore, the use of glass microspheres, hollow ceramic particles, boron nitride and alumina microspheres as thermal conductive fillers is beneficial to reducing the density of the material and improving the impact resistance. Adding a small amount of aromatic isocyanate is beneficial to improving weather resistance and stability. At the same time, since fluoroaniline has good anti-corrosion properties and polyethylene glycol has good anti-fouling properties, the anti-corrosion and anti-fouling properties of polydimethylsiloxane can be improved as a whole.

[0007] Preferably, the mass percentages of TCPP, TEP and organic phosphate are (18-22):(8-12):(1-3).

[0008] Since TCPP, as a porphine derivative, can form a carbon layer at high temperature, TEP and organic phosphate can promote the formation of the carbon layer by forming phosphoric acid. These carbon layers can isolate oxygen and heat and reduce the possibility of material combustion. Combining TCPP, TEP and organic phosphate in the above proportion is conducive to obtaining a higher flame retardant grade, and the smoke and toxic gas generated during combustion are less than those of halogen flame retardants, which is more environmentally friendly.

[0009] Preferably, the modified polydimethylsiloxane comprises the following raw materials: 5g-7g polydimethylsiloxane, 5g-7g modified fluoroaniline, 0.7g-1.54g sodium dodecylbenzene sulfonate, 2.3g-4.43g polyethylene glycol octylphenyl ether, 2g-3.1g n-butanol, 0.5ml-0.6ml hydrochloric acid, and 4ml-8ml ammonium persulfate solution.

[0010] Due to its low surface energy, high flexibility, and smoothness, polydimethylsiloxane is often used in anti-fouling and anti-corrosion. However, the anti-fouling effect of polydimethylsiloxane under static conditions is not ideal, which also limits the application of polydimethylsiloxane. The fluorine atoms in fluoroaniline have extremely high electronegativity, which enables fluoroaniline to form a tight and stable adsorption layer on the metal surface. Therefore, when the battery module is in a humid environment, such as the battery module installed on the pole of a solar street lamp, when it encounters the rainy season, the surrounding air is in a humid state, and the surface of the battery module of the solar street lamp is not easy to attach microorganisms. In addition, the modified fluoroaniline has good anti-fouling properties, which is beneficial to improve the anti-fouling properties of polydimethylsiloxane.

[0011] Preferably, the modified polydimethylsiloxane is prepared by the following preparation method: 0.7g-1.54g of sodium dodecylbenzene sulfonate, 2.3g-4.43g of polyethylene glycol octylphenyl ether, and 2g-3.1g of n-butanol are weighed and mixed, and then 5g-7g of modified fluoroaniline and 5g-7g of polydimethylsiloxane are added, and stirred for 25-35min until the mixture forms a uniform solution, and then 0.5ml-0.6ml of hydrochloric acid is slowly added dropwise, and then 4ml-8ml of ammonium persulfate solution is slowly added dropwise, and stirred at 15-25°C for 5-7h, and then filtered and washed, and the filtered product is placed in an oven at 55-65°C and dried for 22-26h to obtain the modified polydimethylsiloxane.

[0012] Preferably, the modified fluoroaniline comprises the following raw materials: 1g-3g fluoroaniline, 0.1g-0.3g polyethylene glycol-loaded ferrosoferric oxide nanoparticles, 220ml-260ml N,N-dimethylformamide, and 0.5g-1.5g dicyclohexylcarbodiimide.

[0013] Since polyethylene glycol and its derivatives can effectively reduce biological contamination caused by protein adhesion on the surface of materials, and are non-toxic, non-antigenic and non-immunogenic, and also have good biocompatibility, polyethylene glycol has good antifouling properties. Therefore, attaching polyethylene glycol to fluoroaniline is beneficial to improving the overall antifouling properties of fluoroaniline.

[0014] Preferably, the modified fluoroaniline is prepared by the following preparation method: weighing 0.1g-0.3g of polyethylene glycol-loaded ferrosoferric oxide nanoparticles and 220ml-260ml of N,N-dimethylformamide, ultrasonically dispersing the mixed solution for 2-3h, then weighing 1g-3g of fluoroaniline and 0.5g-1.5g of dicyclohexylcarbodiimide and adding them to the mixed dispersion, continuing ultrasonication for 0.3-0.7h, reacting in an oil bath at 85-95°C for 46-50h, after the reaction is completed, cooling the mixed solution, centrifuging to remove the upper layer of liquid, repeatedly washing the lower layer of solid matter with ethanol and deionized water, centrifuging until the upper layer of liquid is colorless, and then freeze-drying for 22-26h to obtain the modified fluoroaniline.

[0015] Preferably, the polyethylene glycol-loaded ferrosoferric oxide nanoparticles include the following raw materials: 1g-3g polyethylene glycol, 3g-5g ferrosoferric oxide nanoparticles, 85ml-95ml deionized water, 10g-14g 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 8g-12g N-hydroxysuccinimide.

[0016] Since the ferroferric oxide nanoparticles have a large specific surface area, polyethylene glycol can be easily loaded on the surface of the ferroferric oxide nanoparticles. At the same time, the ferroferric oxide nanoparticles, as magnetic nanoparticles, have targeting properties, so that the polyethylene glycol loaded on the surface of the ferroferric oxide nanoparticles can be grafted onto fluoroaniline at a specific position.

[0017] Preferably, the polyethylene glycol-loaded ferrosoferric oxide nanoparticles are prepared by the following preparation method: weighing 3g-5g of ferrosoferric oxide nanoparticles and ultrasonically dispersing them in 85ml-95ml of deionized water, then adding 10g-14g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 8g-12g of N-hydroxysuccinimide and 1g-3g of polyethylene glycol, continuing ultrasonic dispersion for 0.5-1.5h, magnetically stirring at 15-25°C for 22-26h, applying an external magnetic field to collect black matter, washing with deionized water for 4-6 times, and vacuum drying at 15-25°C for 10-14h to obtain polyethylene glycol-loaded ferrosoferric oxide nanoparticles.

[0018] In a second aspect, the present application provides a method for preparing a highly efficient, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for a battery module, using the following technical solution: A method for preparing a highly efficient, heat-conductive, environmentally friendly, flame-retardant polyurethane foam potting material for a battery module comprises the following steps: S1: Mix component A and component B in a mass ratio of (0.5-1.5):(0.2-1.8), and stir at 20-30°C and 750-850r / min for 0.5-1.5h to obtain a mixed solution; S2: Inject the mixed liquid into the gap of the battery module shell, complete the potting within 0.5-1.5 minutes, and the demoulding time is 10-15 minutes at 15-25℃.

[0019] In summary, this application has the following beneficial effects: 1. The ternary flame retardant system consisting of TCPP, TEP and organic phosphate ester is halogen-free, which improves the environmental friendliness of the potting material. When the potting material is subjected to high temperature, TCPP, TEP and organic phosphate ester will begin to decompose, releasing phosphoric acid and its derivatives, so that the potting material forms a dense elastic layer at high temperature, thereby blocking oxygen and isolating the fire source.

[0020] At the same time, glass microspheres and hollow ceramic particles are hollow structures, alumina microspheres have a porous structure, and the flaky structure of boron nitride can form a layered structure in the material. Therefore, the use of glass microspheres, hollow ceramic particles, boron nitride and alumina microspheres as thermal conductive fillers is beneficial to reducing the density of the material and improving the impact resistance. Adding a small amount of aromatic isocyanate is beneficial to improving weather resistance and stability. At the same time, since fluoroaniline has good anti-corrosion properties and polyethylene glycol has good anti-fouling properties, the anti-corrosion and anti-fouling properties of polydimethylsiloxane can be improved as a whole.

[0021] 2. TCPP, as a porphine derivative, can form a carbon layer at high temperature. TEP and organic phosphate can promote the formation of the carbon layer by forming phosphoric acid. These carbon layers can isolate oxygen and heat and reduce the possibility of material combustion. Combining TCPP, TEP and organic phosphate in the above proportion is conducive to obtaining a higher flame retardant grade. Compared with halogen flame retardants, the smoke and toxic gas generated during combustion are less and more environmentally friendly.

[0022] 3. Polydimethylsiloxane is often used in anti-fouling and anti-corrosion due to its low surface energy, high flexibility and smoothness. However, the anti-fouling effect of polydimethylsiloxane under static conditions is not ideal, which also limits the application of polydimethylsiloxane. The fluorine atoms in fluoroaniline have extremely high electronegativity, which enables fluoroaniline to form a tight and stable adsorption layer on the metal surface. Therefore, when the battery module is in a humid environment, such as the battery module installed on the pole of a solar street lamp, when it encounters the rainy season, the surrounding air is in a humid state, and the surface of the battery module of the solar street lamp is not easy to attach microorganisms. In addition, the modified fluoroaniline has good anti-fouling performance, which is beneficial to improve the anti-fouling performance of polydimethylsiloxane. DETAILED DESCRIPTION

[0023] The present application is further described in detail below in conjunction with Examples 1 to 11 and Comparative Examples 1 to 3.

[0024] raw material

[0025] Aliphatic isocyanate Shanghai Zhenlishi Network Technology Co., Ltd.; aromatic isocyanate Shandong Xinyihong Chemical Technology Co., Ltd.; high resilience polyether polyol Shandong Shengyong Biotechnology Co., Ltd.; environmentally friendly flame retardant polyester polyol Beijing Baiyuan Chemical Co., Ltd.; TCPP CAS: 13674-84-5; TEP CAS: 78-40-0; organic phosphate Pande (Shanghai) International Trade Co., Ltd.; glass microbeads Lingshou Erlei Mining Co., Ltd.; hollow ceramic microparticles Xinyang Industrial City Huasheng Insulation Factory; boron nitride CAS: 10043-11-5; alumina microspheres Shandong Xuanwei New Materials Co., Ltd.; polydimethylsiloxane Hangzhou Sloan Materials Technology Co., Ltd.; sodium dodecylbenzene sulfonate CAS: 25155-30-0; polyethylene glycol octylphenyl ether CAS: 9002-93-1; n-butanol CAS: 71-36-3; hydrochloric acid CAS: 7647-01-0; Ammonium sulfate CAS: 7727-54-0; Fluoroaniline Aladdin Industries (Shanghai, China); N,N-dimethylformamide Aladdin Industries (Shanghai, China); Dicyclohexylcarbodiimide CAS: 538-75-0; Polyethylene glycol CAS: 25322-68-3; Ferroferric oxide nanoparticles Hangzhou Jikang New Materials Co., Ltd.; Deionized water CAS: 7732-18-5; 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride CAS: 25952-53-8; N-Hydroxysuccinimide Aladdin Industries (Shanghai, China).

[0026] Example 1

[0027] A high-efficiency, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for a battery module, comprising the following raw materials in percentage by mass: 27.5% aliphatic isocyanate, 2% aromatic isocyanate, 5% high-resilience polyether polyol, 3% environmentally friendly flame-retardant polyester polyol, 32% halogen-free flame retardant, 25% thermally conductive filler, and 6% modified polydimethylsiloxane.

[0028] Specifically, the preparation method of the high-efficiency thermally conductive and environmentally friendly flame-retardant polyurethane foam potting material for battery modules comprises the following steps: S1: Weigh 4 g of ferroferric oxide nanoparticles and ultrasonically disperse them in 90 ml of deionized water, then add 12 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 10 g of N-hydroxysuccinimide and 2 g of polyethylene glycol, continue ultrasonic dispersion for 1 h, magnetically stir at 20 ° C for 24 h, apply an external magnetic field to collect the black material, wash it with deionized water 5 times, and then vacuum dry it at 20 ° C for 12 h to obtain polyethylene glycol-loaded ferroferric oxide nanoparticles; S2: Weigh 0.2g of polyethylene glycol-loaded ferroferric oxide nanoparticles and 240ml of N,N-dimethylformamide, and ultrasonically disperse the mixed solution for 2.5h. Then weigh 2g of fluoroaniline and 1g of dicyclohexylcarbodiimide and add them to the mixed dispersion, continue ultrasonication for 0.5h, and react in a 90℃ oil bath for 48h. After the reaction is completed, the mixed solution is cooled and centrifuged to remove the upper layer of liquid. The lower solid matter is repeatedly washed with ethanol and water and centrifuged until the upper layer of liquid is colorless, and then freeze-dried for 24h to obtain modified fluoroaniline; S3: 1.12 g of sodium dodecylbenzene sulfonate, 3.37 g of polyethylene glycol octylphenyl ether, and 2.55 g of n-butanol were weighed and mixed, and then 6 g of modified fluoroaniline and 6 g of polydimethylsiloxane were added, and stirred for 30 min until the mixture formed a uniform solution, and then 0.55 ml of hydrochloric acid was slowly added dropwise, and then 6 ml of ammonium persulfate solution was slowly added dropwise, and stirred at 20° C. for 6 h, and then filtered and washed, and the filtered product was placed in an oven at 60° C. and dried for 24 h to obtain modified polydimethylsiloxane; S4: Component A and component B are mixed in a mass ratio of 1:1, and stirred at 25°C and 800 r / min for 1 h to obtain a mixed solution; Wherein, component A is a mixture of 27.5% aliphatic isocyanate and 2% aromatic isocyanate; Component B is a mixture of 5% high resilience polyether polyol, 3% environmentally friendly flame retardant polyester polyol, 32% halogen-free flame retardant, 25% thermal conductive filler, and 6% modified polydimethylsiloxane; 32% halogen-free flame retardant is a ternary flame retardant system consisting of TCPP, TEP and organic phosphate in a mass percentage of 20:10:2; 25% thermally conductive filler contains glass microspheres, hollow ceramic particles, boron nitride and alumina microspheres; S5: Inject the mixed liquid into the gap of the battery module shell and complete the potting within 1 minute. The demolding time is 12.5 minutes at 20°C.

[0029] Example 2-Example 3 The difference from Example 1 is that the mass percentages of the components of the high-efficiency, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for the battery module are different, as shown in Table 1.

[0030] Table 1 Mass percentage of each component of the high-efficiency thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules in Examples 1 to 3 (%)

[0031] Example 4 The difference from Example 1 is that the mass percentages of TCPP, TEP and organic phosphate are 18:12:3.

[0032] Example 5

[0033] The difference from Example 1 is that the mass percentage of component A to component B is 0.5:1.8.

[0034] Example 6-Example 7 The difference from Example 1 is that the added amounts of the components of the polyethylene glycol-loaded ferrosoferric oxide nanoparticles are different, as shown in Table 2.

[0035] Table 2 The amount of each component added in polyethylene glycol-loaded ferroferric oxide nanoparticles in Example 1 and Example 6-Example 7

[0036] Example 8-Example 9 The difference from Example 1 is that the added amounts of the various components of the modified fluoroaniline are different, as shown in Table 3.

[0037] Table 3 Addition amount of each component of modified fluoroaniline in Example 1 and Example 8-Example 9

[0038] Example 10-Example 11 The difference from Example 1 is that the added amounts of the various components of the modified polydimethylsiloxane are different, as shown in Table 4.

[0039] Table 4 Addition amount of each component of modified polydimethylsiloxane in Example 1 and Example 10-Example 11

[0040] Comparative Example 1 The difference from Example 1 is that the halogen-free flame retardant is replaced by an equal amount of halogen flame retardant.

[0041] Comparative Example 2 The difference from Example 1 is that no modified polydimethylsiloxane is added.

[0042] Comparative Example 3 The difference from Example 1 is that polyethylene glycol is no longer added to load the ferrosoferric oxide nanoparticles.

[0043] Performance testing 1. Environmental performance Three samples were taken from Examples 1 to 11 and Comparative Examples 1 to 3 respectively, and the smoke generation rate was tested according to GB / T20284-2006 "Monomer Combustion Test for Building Materials or Products", the UL94 flame retardant grade of the samples was tested, and the thermal conductivity of the samples was tested according to ASTM D5470, and the average value was taken.

[0044] The test data are shown in Table 5.

[0045] Table 5 High temperature resistance test table of Example 1-Example 11 and Comparative Example 1-Comparative Example 3

[0046] 2. Anti-corrosion and anti-fouling performance Three samples were taken from Examples 1 to 11 and Comparative Examples 1 to 3, respectively, and the anti-corrosion performance was tested according to GB / T2423.17-2008 "Environmental testing for electrical and electronic products Part 2: Test method Test Ka: Salt spray"; 2 mL of sterilized Sabouraud culture solution and 2 drops of bacteria with a concentration of 1.5×10 8 CFU / mL bacterial solution, mix thoroughly and then dilute 1 times, evenly dip the polyurethane membrane, place it in a 37℃ incubator for 24 hours to test the antifouling performance, check the number of bacterial colonies under a microscope, calculate the antibacterial rate, and take the average value.

[0047] The test data are shown in Table 6.

[0048] Table 6 Anticorrosion and antifouling performance test table of Example 1 to Example 11 and Comparative Example 1 to Comparative Example 3

[0049] Combining Example 1 and Comparative Example 1 and Tables 5 and 6, it can be seen that, relative to Example 1, the UL94 grade of Comparative Example 1 is V0. At the same time, the smoke generation rate of Comparative Example 1 is greatly increased, the thermal conductivity of Comparative Example 1 is greatly decreased, the anti-corrosion area of ​​Comparative Example 1 after 72 hours is increased, and the antibacterial rate of Comparative Example 1 is also decreased. This shows that, relative to the addition of halogen flame retardants, the addition of halogen-free flame retardants can effectively improve the environmental protection performance, flame retardant performance and thermal conductivity of the potting material, and the halogen-free flame retardant can improve the anti-corrosion and anti-fouling properties of the potting material to a certain extent.

[0050] The reason is that the halogen-free flame retardant of the ternary flame retardant system composed of TCPP, TEP and organic phosphate does not contain halogen, which improves the environmental friendliness of the potting material. When the potting material is subjected to high temperature, TCPP, TEP and organic phosphate will begin to decompose, releasing phosphoric acid and its derivatives, so that the potting material forms a dense elastic layer at high temperature, thereby blocking oxygen and isolating the fire source.

[0051] At the same time, glass microspheres and hollow ceramic particles are hollow structures, alumina microspheres have a porous structure, and the flaky structure of boron nitride can form a layered structure in the material. Therefore, the use of glass microspheres, hollow ceramic particles, boron nitride and alumina microspheres as thermal conductive fillers is beneficial to reducing the density of the material and improving the impact resistance. Adding a small amount of aromatic isocyanate is beneficial to improving weather resistance and stability. At the same time, since fluoroaniline has good anti-corrosion properties and polyethylene glycol has good anti-fouling properties, the anti-corrosion and anti-fouling properties of polydimethylsiloxane can be improved as a whole.

[0052] Combining Example 1 and Comparative Example 2 and Tables 5 and 6, it can be seen that, relative to Example 1, the UL94 grade of Comparative Example 2 is V0. At the same time, the smoke generation rate of Comparative Example 2 is increased, the thermal conductivity of Comparative Example 2 is decreased, the anti-corrosion area of ​​Comparative Example 2 is greatly increased after 72 hours, and the antibacterial rate of Comparative Example 1 is also greatly decreased. This shows that the addition of modified polydimethylsiloxane is not easy to affect the flame retardant properties of the potting material. However, the addition of modified polydimethylsiloxane can effectively improve the anti-corrosion and anti-fouling properties of the potting material, and the addition of modified polydimethylsiloxane affects the environmental protection and thermal conductivity of the potting material to a certain extent.

[0053] The reason is that polydimethylsiloxane is often used in anti-fouling and anti-corrosion due to its low surface energy, high flexibility, smoothness, etc. However, the anti-fouling effect of polydimethylsiloxane under static conditions is not ideal, which also limits the application of polydimethylsiloxane. The fluorine atoms in fluoroaniline have good hydrophobicity and excellent anti-adhesion properties, so that fluoroaniline can reduce the possibility of hydrolysis reaction and reduce the possibility of bacteria, fungi and other microorganisms adhering to the surface of the material. The reaction of fluoroaniline with polydimethylsiloxane is beneficial to improving the anti-corrosion performance of polydimethylsiloxane, and the modified fluoroaniline has good anti-fouling performance, which is beneficial to improving the anti-fouling performance of polydimethylsiloxane.

[0054] Combining Example 1 and Comparative Example 3 and Tables 5-6, it can be seen that, relative to Example 1, the UL94 grade of Comparative Example 3 is V0. At the same time, the smoke generation rate of Comparative Example 3 is increased, the thermal conductivity of Comparative Example 3 is decreased, the anti-corrosion area of ​​Comparative Example 3 after 72 hours is greatly increased, and the antibacterial rate of Comparative Example 3 is also greatly decreased. This shows that the addition of polyethylene glycol-loaded ferrosoferric oxide nanoparticles is not easy to affect the flame retardant properties of the potting material. However, the addition of polyethylene glycol-loaded ferrosoferric oxide nanoparticles can effectively improve the anti-corrosion and anti-fouling properties of the potting material, and the addition of polyethylene glycol-loaded ferrosoferric oxide nanoparticles affects the environmental protection and thermal conductivity of the potting material to a certain extent.

[0055] Combining Example 1 and Example 2-Example 3 and Table 5-Table 6, it can be seen that, relative to Example 1, the UL94 grade of Example 2 and Example 3 is VO, but the smoke generation rate of Example 2 and Example 3 is increased, and the thermal conductivity of Example 2 and Example 3 is decreased. At the same time, the anti-corrosion area of ​​Example 2 and Example 3 after 72 hours is increased, and the antibacterial rate of Example 2 and Example 3 is also decreased. This shows that the mass percentage of each component of the potting material is not easy to affect the flame retardant properties of the potting material, but affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material to a certain extent.

[0056] Combining Example 1 and Example 4 and Tables 5 and 6, it can be seen that, relative to Example 1, the UL94 grade of Example 4 is V0, but the smoke generation rate of Example 4 increases, the thermal conductivity of Example 4 decreases, and the anti-corrosion area of ​​Example 4 increases slightly after 72 hours, and the antibacterial rate of Example 4 also decreases slightly. This shows that the mass percentage of TCPP, TEP and organophosphate ester is not easy to affect the flame retardant properties of the potting material, but affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material.

[0057] From Example 1 and Example 5 and Tables 5 to 6, it can be seen that, relative to Example 1, the UL94 grade of Example 5 is V0, but the smoke generation rate of Example 5 increases, the thermal conductivity of Example 5 decreases, and the anti-corrosion area of ​​Example 5 increases slightly after 72 hours, and the antibacterial rate of Example 5 also decreases slightly. This shows that the mass percentage of component A and component B is not easy to affect the flame retardant properties of the potting material, but affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material.

[0058] Combining Example 1 and Example 6-Example 7 and Table 5-Table 6, it can be seen that, relative to Example 1, the UL94 ratings of Example 6 and Example 7 are both VO, but the smoke generation rates of Example 6 and Example 7 are both increased, and the thermal conductivity of Example 6 and Example 7 is both decreased. At the same time, the anti-corrosion area of ​​Example 6 and Example 7 after 72 hours is increased, and the antibacterial rate of Example 6 and Example 7 is also decreased. This shows that the addition amount of each component of the polyethylene glycol-loaded ferrosoferric oxide nanoparticles is not easy to affect the flame retardant properties of the potting material, but affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material to a certain extent.

[0059] Combining Example 1 and Example 8-Example 9 and Table 5-Table 6, it can be seen that, relative to Example 1, the UL94 rating of Example 8 and Example 9 is VO, but the smoke generation rate of Example 8 and Example 9 is increased, and the thermal conductivity of Example 8 and Example 9 is decreased. At the same time, the anti-corrosion area of ​​Example 8 and Example 9 after 72 hours is greatly increased, and the antibacterial rate of Example 8 and Example 9 is also greatly decreased. This shows that the addition amount of each component of the modified fluoroaniline is not easy to affect the flame retardant properties of the potting material, but affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material to a certain extent, especially the anti-corrosion performance and anti-fouling performance of the potting material.

[0060] Combining Example 1 and Example 10-Example 11 and Table 5-Table 6, it can be seen that, relative to Example 1, the UL94 rating of Example 10 and Example 11 is VO, but the smoke generation rate of Example 10 and Example 11 is increased, and the thermal conductivity of Example 10 and Example 11 is decreased. At the same time, the anti-corrosion area of ​​Example 10 and Example 11 after 72 hours is greatly increased, and the antibacterial rate of Example 10 and Example 11 is also greatly decreased. This shows that the addition amount of each component of the modified polydimethylsiloxane is not easy to affect the flame retardant properties of the potting material, but to a certain extent affects the environmental protection performance, thermal conductivity, anti-corrosion performance and anti-fouling performance of the potting material, especially the anti-corrosion performance and anti-fouling performance of the potting material.

[0061] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly efficient, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules, characterized in that: It is made by mixing component A and component B in the mass percentage of (0.5-1.5): (0.2-1.8): Component A includes the following raw materials in percentage by mass: 15%-40% aliphatic isocyanate, 1%-3% aromatic isocyanate; Component B includes the following raw materials in percentage by mass: 4%-6% high resilience polyether polyol, 2%-4% environmentally friendly flame retardant polyester polyol, 27%-37% halogen-free flame retardant, 20%-30% thermal conductive filler, and 5%-7% modified polydimethylsiloxane; The halogen-free flame retardant is a ternary flame retardant system consisting of TCPP, TEP and organic phosphate; The thermally conductive filler contains glass microspheres, hollow ceramic microparticles, boron nitride and alumina microspheres; The modified polydimethylsiloxane contains fluoroaniline and polyethylene glycol.

2. According to claim 1, a highly efficient, heat-conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules is characterized by: The mass percentages of the TCPP, TEP and organic phosphate are (18-22):(8-12):(1-3).

3. The high-efficiency, thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 1, characterized in that: The modified polydimethylsiloxane comprises the following raw materials: 5g-7g polydimethylsiloxane, 5g-7g modified fluoroaniline, 0.7g-1.54g sodium dodecylbenzene sulfonate, 2.3g-4.43g polyethylene glycol octylphenyl ether, 2g-3.1g n-butanol, 0.5ml-0.6ml hydrochloric acid, and 4ml-8ml ammonium persulfate solution.

4. The high-efficiency, heat-conducting, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 3, characterized in that: The modified polydimethylsiloxane is prepared by the following preparation method: 0.7g-1.54g of sodium dodecylbenzene sulfonate, 2.3g-4.43g of polyethylene glycol octylphenyl ether, and 2g-3.1g of n-butanol are weighed and mixed, then 5g-7g of modified fluoroaniline and 5g-7g of polydimethylsiloxane are added, and stirred for 25-35min until the mixture forms a uniform solution, then 0.5ml-0.6ml of hydrochloric acid is slowly added dropwise, then 4ml-8ml of ammonium persulfate solution is slowly added dropwise, and the mixture is stirred at 15-25°C for 5-7h, then filtered and washed, and the filtered product is placed in an oven at 55-65°C for drying for 22-26h to obtain the modified polydimethylsiloxane.

5. The high-efficiency, heat-conducting, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 4, characterized in that: The modified fluoroaniline comprises the following raw materials: 1g-3g fluoroaniline, 0.1g-0.3g polyethylene glycol-loaded ferrosoferric oxide nanoparticles, 220ml-260ml N,N-dimethylformamide, and 0.5g-1.5g dicyclohexylcarbodiimide.

6. The high-efficiency heat-conducting, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 5, characterized in that: The modified fluoroaniline is prepared by the following preparation method: 0.1g-0.3g of polyethylene glycol-loaded ferrosoferric oxide nanoparticles and 220ml-260ml of N,N-dimethylformamide are weighed, the mixed solution is ultrasonically dispersed for 2-3h, then 1g-3g of fluoroaniline and 0.5g-1.5g of dicyclohexylcarbodiimide are weighed and added to the mixed dispersion, the ultrasonication is continued for 0.3-0.7h, and the mixture is reacted in an oil bath pot at 85-95°C for 46-50h. After the reaction is completed, the mixed solution is cooled, centrifuged to remove the upper layer of liquid, the lower layer of solid matter is repeatedly washed with ethanol and deionized water and centrifuged until the upper layer of liquid is colorless, and then freeze-dried for 22-26h to obtain the modified fluoroaniline.

7. The high-efficiency thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 6, characterized in that: The polyethylene glycol-loaded ferrosoferric oxide nanoparticles include the following raw materials: 1g-3g polyethylene glycol, 3g-5g ferrosoferric oxide nanoparticles, 85ml-95ml deionized water, 10g-14g 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 8g-12g N-hydroxysuccinimide.

8. The high-efficiency, heat-conducting, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules according to claim 7, characterized in that: The polyethylene glycol-loaded ferrosoferric oxide nanoparticles are prepared by the following preparation method: weighing 3g-5g of ferrosoferric oxide nanoparticles and ultrasonically dispersing them in 85ml-95ml of deionized water, then adding 10g-14g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, 8g-12g of N-hydroxysuccinimide and 1g-3g of polyethylene glycol, continuing ultrasonic dispersion for 0.5-1.5h, magnetically stirring at 15-25°C for 22-26h, applying an external magnetic field to collect black matter, washing with deionized water for 4-6 times, and vacuum drying at 15-25°C for 10-14h to obtain polyethylene glycol-loaded ferrosoferric oxide nanoparticles.

9. A preparation method for preparing the high-efficiency thermally conductive, environmentally friendly, flame-retardant polyurethane foam potting material for battery modules as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: S1: Mix component A and component B in a mass ratio of (0.5-1.5):(0.2-1.8), and stir at 20-30°C and 750-850r / min for 0.5-1.5h to obtain a mixed solution; S2: Inject the mixed liquid into the gap of the battery module shell, complete the potting within 0.5-1.5 minutes, and the demoulding time is 10-15 minutes at 15-25℃.

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