Production and application of novel new energy battery fireproof insulating material

Abstract

The invention discloses production and application of a novel new energy battery fireproof insulating material, and belongs to the technical field of new energy battery materials. Comprising the following steps: carrying out melt blending on pretreated PA, a modified silane coupling agent, dicumyl peroxide and an antioxidant 1010, granulating, carrying out injection molding, and carrying out irradiation modification to obtain the fireproof insulating material. The novel new energy battery fireproof insulating material obtained through modification not only has fireproof insulating performance, but also improves stability.

Description

Technical Field

[0001] This invention belongs to the field of new energy battery materials technology, specifically relating to the production and application of a novel fireproof and insulating material for new energy batteries. Background Technology

[0002] Polyamide (PA) is a high-performance synthetic polymer material. Its main chain structure contains repeating amide groups (-CONH-), which form linear or semi-aromatic polymers through polycondensation. Due to the strong polar amide bonds in its molecular chain, PA materials exhibit excellent mechanical strength, heat resistance, wear resistance, and chemical stability, and are widely used in automobiles, electronics, textiles, and other fields. With the rapid development of new energy vehicles, the safety of power batteries has received increasing attention, especially the demand for fireproof insulation of battery packs. At present, the fireproof insulation material widely used in battery packs is mainly mica board. Its preparation process requires first breaking down mica ore into mica paper, and then molding it through a molding process. However, this process has two major problems: (1) the molding production efficiency is extremely low, relying on a lot of manual operation; (2) mica paper is brittle and has poor toughness, making it difficult to process into boards with complex structures, which limits its optimized design in battery packs. Against this background, PA materials, due to their good processability, high toughness, and molding efficiency, show potential advantages in the application of fireproof insulation materials for new energy batteries. PA can be rapidly molded into complex structural parts using efficient processes such as injection molding, and it also possesses certain heat resistance and insulation properties, which helps improve production efficiency and design flexibility. However, PA itself has insufficient fire resistance, making it difficult to meet the high flame retardant and heat insulation standards required for battery packs. Therefore, it needs to be modified to improve its fire resistance and insulation properties to meet the safety requirements of power batteries for new energy vehicles.

[0003] Patent CN116844758B discloses a mica insulating material for new energy vehicle battery cells, its preparation method, and its application. This invention uses a treatment liquid, hollow silica microsphere powder, magnesium hydroxide powder, and polyurethane adhesive as raw materials. Specifically, mica powder, high-temperature resistant silicone rubber, and alkali-free glass cloth short fibers are mixed, and a silane coupling agent is added to obtain the insulating treatment liquid. The insulating treatment liquid is heated to 50℃~70℃, and then hollow silica microsphere powder, magnesium hydroxide powder, and polyurethane adhesive are added. After stirring, a mixture of the insulating material is obtained. The patent above improves the insulation and heat insulation performance of new energy batteries by adding high-temperature resistant silicone rubber and alkali-free glass cloth short fibers. Although silicone rubber has high-temperature resistance, if the local temperature exceeds its tolerance limit during battery thermal runaway, it may decompose and fail, losing its insulating and adhesive properties. Simultaneously, silicone rubber is prone to hydrolysis or oxidation in high-temperature and high-humidity environments, leading to aging and affecting the material's service life.

[0004] Therefore, it is of great significance to improve the fireproof and insulation performance of fireproof insulation materials while maintaining their stability. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention utilizes a method where a silane coupling agent undergoes a hydrolysis reaction with anhydrous ethanol to generate silanol, which then undergoes a condensation reaction with PA to form a cross-linked network, enhancing the inorganic-organic interface bonding. Simultaneously, dicumyl peroxide acts as an initiator, decomposing upon heating to generate free radicals that initiate the reaction between the silane coupling agent and PA. These free radicals attack the C=C double bonds of the silane coupling agent, forming an active intermediate. These free radicals can further react with the -NH- or -CH2- groups of the PA chain to form covalent cross-links. Secondly, the surface of nano-silica is rich in hydroxyl groups, which can co-condense with the silanol obtained from the hydrolysis of the silane coupling agent to form chemical bonds (Si-O-Si), promoting the condensation reaction between the modified silane coupling agent and PA to form a cross-linked network structure, enhancing fire resistance and insulation performance while improving stability. This solves the technical problems mentioned in the background art. Specifically, the technical solution of this invention includes the following: One objective of this invention is to provide a production method for a novel fire-resistant and insulating material for new energy batteries, the production of which includes the following steps: Pretreated PA particles are obtained by heating them to 80°C and drying them for 4 hours. Pretreated PA, modified silane coupling agent, dicumyl peroxide and antioxidant 1010 are melt-blended in a weight ratio of 100:1.5:0.3:0.4, and then granulated, injection molded and irradiated to obtain a fireproof and insulating material.

[0006] Furthermore, the PA particles comprise nylon-66.

[0007] Furthermore, the preparation method of the modified silane coupling agent includes the following steps: A modified silane coupling agent is obtained by mixing and reacting a silane coupling agent suspension and nano-silica at a weight ratio of 0.3~0.5:1.

[0008] Furthermore, the preparation method of the silane coupling agent suspension includes the following steps: A silane coupling agent, deionized water, and anhydrous ethanol were mixed in a weight ratio of 1:0.1 to 0.2:1, the pH was adjusted to 4, and the mixture was heated to 40°C for 3 hours to obtain a silane coupling agent suspension.

[0009] Furthermore, the silane coupling agent includes vinyltrimethoxysilane.

[0010] Furthermore, the particle size of the nano-silica is 30 nm.

[0011] Furthermore, the melt blending conditions include a temperature of 260°C, a time of 10 min, and a rotation speed of 80 r / min.

[0012] Furthermore, the granulation conditions include a particle size of 2 mm.

[0013] Furthermore, the injection molding conditions include a holding pressure of 90 MPa, a holding time of 10 s, and an injection temperature of 270°C.

[0014] Furthermore, the conditions for the irradiation modification include an irradiation energy of 150 keV, an irradiation dose of 100 kGy, and an irradiation time of 20 s.

[0015] The second objective of this invention is to provide an application of a fire-resistant insulating material obtained through the production of a novel new energy battery fire-resistant insulating material in the field of battery fire-resistant insulation.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention first utilizes the hydrolysis of a silane coupling agent in anhydrous ethanol to generate silanol. The silanol undergoes a condensation reaction with PA to form covalent bonds, constructing a cross-linked network structure. Simultaneously, dicumyl peroxide acts as an initiator, decomposing under heating conditions to generate free radicals. These free radicals preferentially attack the C=C double bonds of the silane coupling agent, forming active silane free radicals, which then combine with -NH- or -CH2- groups on the PA molecular chain to form a PA-silane covalent cross-linked structure. Furthermore, the modified silane coupling agent can also undergo a condensation reaction with PA, further strengthening the cross-linked network and promoting the bonding of nano-silica with PA, forming a cross-linked network structure. This cross-linked network structure not only improves the fire-resistant and insulating properties of the fire-resistant insulating material but also enhances its stability, collectively constructing a fire-resistant and insulating material with fire-resistant and insulating properties for use in the field of battery fire-resistant insulation. Detailed Implementation

[0017] The technical solution of the present invention will be clearly and completely described below through embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Unless otherwise stated, all raw materials and reagents used in this invention are commercially available or can be produced by known methods.

[0019] Preparation Example 1: The preparation method of the silane coupling agent suspension specifically includes the following steps: Weigh 1 part by weight of vinyltrimethoxysilane, 0.1 part by weight of deionized water and 1 part by weight of anhydrous ethanol, mix them, adjust the pH to 4, heat to 40°C and stir for 3 hours to obtain a silane coupling agent suspension.

[0020] Preparation Example 2: The preparation method of the silane coupling agent suspension specifically includes the following steps: Weigh 1 part by weight of vinyltrimethoxysilane, 0.2 parts by weight of deionized water and 1 part by weight of anhydrous ethanol, mix them, adjust the pH to 4, heat to 40°C and stir for 3 hours to obtain a silane coupling agent suspension.

[0021] Preparation Example 3: The preparation method of the modified silane coupling agent specifically includes the following steps: Weigh 0.3 parts by weight of the silane coupling agent suspension prepared in Example 1 and 1 part by weight of nano-silica with a particle size of 30 nm and place them in a reaction vessel and mix. First, heat to 30°C at 300 r / min and stir for 15 min; then heat to 70°C at 800 r / min and stir for 3 h to obtain the modified silane coupling agent.

[0022] Preparation Example 4: The preparation method of the modified silane coupling agent specifically includes the following steps: Weigh 0.5 parts by weight of the silane coupling agent suspension prepared in Example 1 and 1 part by weight of nano-silica with a particle size of 30 nm and place them in a reaction vessel and mix. First, heat to 30°C at 300 r / min and stir for 15 min; then heat to 70°C at 800 r / min and stir for 3 h to obtain the modified silane coupling agent.

[0023] Preparation Example 5: The preparation method of the modified silane coupling agent specifically includes the following steps: Weigh 0.3 parts by weight of the silane coupling agent suspension prepared in Example 2 and 1 part by weight of nano-silica with a particle size of 30 nm and place them in a reaction vessel and mix. First, heat to 30°C at 300 r / min and stir for 15 min; then heat to 70°C at 800 r / min and stir for 3 h to obtain the modified silane coupling agent.

[0024] Preparation Example 6: The preparation method of the modified silane coupling agent specifically includes the following steps: 0.5 parts by weight of the silane coupling agent suspension prepared in Example 2 and 1 part by weight of nano-silica with a particle size of 30 nm were placed in a reaction vessel and mixed. First, the mixture was heated to 30 °C at a speed of 300 r / min and stirred for 15 min; then, it was heated to 70 °C at a speed of 800 r / min and stirred for 3 h to obtain the modified silane coupling agent.

[0025] Preparation Example 7: The preparation method of the modified silane coupling agent specifically includes the following steps: One part by weight of the silane coupling agent suspension prepared in Example 1 and one part by weight of nano-silica with a particle size of 30 nm were placed in a reaction vessel and mixed. The mixture was first heated to 30 °C at a speed of 300 r / min and stirred for 15 min; then heated to 70 °C at a speed of 800 r / min and stirred for 3 h to obtain the modified silane coupling agent.

[0026] Preparation Example 8: The preparation method of the modified silane coupling agent specifically includes the following steps: 0.1 parts by weight of the silane coupling agent suspension prepared in Example 1 and 1 part by weight of nano-silica with a particle size of 30 nm were placed in a reaction vessel and mixed. First, the mixture was heated to 30 °C at a speed of 300 r / min and stirred for 15 min; then, it was heated to 70 °C at a speed of 800 r / min and stirred for 3 h to obtain the modified silane coupling agent.

[0027] Preparation Example 9: The preparation method of the modified silane coupling agent specifically includes the following steps: 0.3 parts by weight of the silane coupling agent suspension prepared in Example 2 and 2 parts by weight of nano-silica with a particle size of 30 nm were placed in a reaction vessel and mixed. First, the mixture was heated to 30 °C and stirred for 15 min at a speed of 300 r / min; then, it was heated to 70 °C and stirred for 3 h at a speed of 800 r / min to obtain the modified silane coupling agent.

[0028] Preparation Example 10: The preparation method of the modified silane coupling agent specifically includes the following steps: 0.3 parts by weight of the silane coupling agent suspension prepared in Example 2 and 0.5 parts by weight of nano-silica with a particle size of 30 nm were placed in a reaction vessel and mixed. The mixture was first heated to 30 °C at 300 r / min and stirred for 15 min; then heated to 70 °C at 800 r / min and stirred for 3 h to obtain the modified silane coupling agent.

[0029] Example 1: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: Using melt blending technology, 100 parts by weight of nylon-66, 1.5 parts by weight of the modified silane coupling agent prepared in Preparation Example 3, 0.3 parts by weight of dicumyl peroxide, and 0.4 parts by weight of antioxidant 1010 were weighed and mixed in an extruder preheated to 100°C. The extruder temperature was then further increased to 260°C, and melt blending was performed at 80 r / min for 10 min. The mixture was then granulated to obtain particles with a size of 2 mm. The particles were placed in a mold preheated to 90°C, and then the temperature was increased to 270°C. The pressure was controlled at 90 MPa, and injection molding was performed for 10 s. After injection molding, the mixture was allowed to cool naturally to room temperature, demolded, and placed on the irradiation platform of an irradiation device. Nitrogen gas was introduced to purge the air, and the irradiation energy was adjusted to 150 keV and the irradiation dose to 100 kGy for 20 s to obtain a fire-resistant insulating material.

[0030] Example 2: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: Using melt blending technology, 100 parts by weight of nylon-66, 1.5 parts by weight of the modified silane coupling agent prepared in Preparation Example 4, 0.3 parts by weight of dicumyl peroxide, and 0.4 parts by weight of antioxidant 1010 were weighed and mixed in an extruder preheated to 100°C. The extruder temperature was then further increased to 260°C, and melt blending was performed at 80 r / min for 10 min. The mixture was then granulated to obtain particles with a size of 2 mm. The particles were placed in a mold preheated to 90°C, and then the temperature was increased to 270°C. The pressure was controlled at 90 MPa, and injection molding was performed for 10 s. After injection molding, the mixture was allowed to cool naturally to room temperature, demolded, and placed on the irradiation platform of an irradiation device. Nitrogen gas was introduced to purge the air, and the irradiation energy was adjusted to 150 keV and the irradiation dose to 100 kGy for 20 s to obtain a fire-resistant insulating material.

[0031] Example 3: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: Using melt blending technology, 100 parts by weight of nylon-66, 1.5 parts by weight of the modified silane coupling agent prepared in Preparation Example 5, 0.3 parts by weight of dicumyl peroxide, and 0.4 parts by weight of antioxidant 1010 were weighed and mixed in an extruder preheated to 100°C. The extruder temperature was then further increased to 260°C, and melt blending was performed at 80 r / min for 10 min. The mixture was then granulated to obtain particles with a size of 2 mm. The particles were placed in a mold preheated to 90°C, and then the temperature was increased to 270°C. The pressure was controlled at 90 MPa, and injection molding was performed for 10 s. After injection molding, the mixture was allowed to cool naturally to room temperature, demolded, and placed on the irradiation platform of an irradiation device. Nitrogen gas was introduced to purge the air, and the irradiation energy was adjusted to 150 keV and the irradiation dose to 100 kGy for 20 s to obtain a fire-resistant insulating material.

[0032] Example 4: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: Using melt blending technology, 100 parts by weight of nylon-66, 1.5 parts by weight of the modified silane coupling agent prepared in Preparation Example 6, 0.3 parts by weight of dicumyl peroxide, and 0.4 parts by weight of antioxidant 1010 were weighed and mixed in an extruder preheated to 100°C. The extruder temperature was then further increased to 260°C, and melt blending was performed at 80 r / min for 10 min. The mixture was then granulated to obtain particles with a size of 2 mm. The particles were placed in a mold preheated to 90°C, and then the temperature was increased to 270°C. The pressure was controlled at 90 MPa, and injection molding was performed for 10 s. After injection molding, the mixture was allowed to cool naturally to room temperature, demolded, and placed on the irradiation platform of an irradiation device. Nitrogen gas was introduced to purge the air, and the irradiation energy was adjusted to 150 keV and the irradiation dose to 100 kGy for 20 s to obtain a fire-resistant insulating material.

[0033] Comparative Example 1: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: The modified silane coupling agent in Example 1 was replaced with the modified silane coupling agent obtained in Preparation Example 7, and the rest of the preparation process was the same as in Example 1.

[0034] Comparative Example 2: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: The modified silane coupling agent in Example 2 was replaced with the modified silane coupling agent obtained in Preparation Example 8, and the rest of the preparation process was the same as in Example 2.

[0035] Comparative Example 3: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: The modified silane coupling agent in Example 3 was replaced with the modified silane coupling agent obtained in Preparation Example 9, and the rest of the preparation process was the same as in Example 3.

[0036] Comparative Example 4: The production of a novel fire-resistant and insulating material for new energy batteries specifically includes the following processes: The modified silane coupling agent in Example 4 was replaced with the modified silane coupling agent obtained in Preparation Example 10, and the rest of the preparation process was the same as in Example 4.

[0037] The fire-resistant insulating materials obtained in Examples 1-4 and Comparative Examples 1-4 were subjected to insulation performance tests in accordance with GB / T1410-2006. The fire-resistant insulating materials obtained in Examples 1-4 and Comparative Examples 1-4 were subjected to tensile property tests according to GB / T1040.1-2018. The fire-resistant insulating materials obtained in Examples 1-4 and Comparative Examples 1-4 were made into flat plates with dimensions of 100mm × 100mm × 2mm. The edges were covered with a metal frame to prevent shrinkage. The samples were fixed using a steel plate support, 10cm away from the flame. The central area of ​​the sample was continuously scorched with a spray gun (scorching temperature maintained at 1200°C ± 50°C) for 30 minutes. Observation was performed to check for burn-through, cracking, or significant deformation. High-temperature resistance tests were then conducted using the methods described above. The results of the insulation performance test, tensile performance test, and high-temperature resistance test are shown in Table 1.

[0038] Table 1 Performance Tests

[0039] The following conclusions can be drawn from Table 1 above: (1) As can be seen from Examples 1 to 4, the fireproof insulation material modified by the present invention not only has good fireproof insulation properties, but also exhibits good tensile properties.

[0040] (2) It can be found through Comparative Example 1 that the test results of the fireproof insulation material modified by the present invention are generally lower than those of corresponding Examples 1 to 4. This may be because excessive silane coupling agent suspension was added to Comparative Example 1, and the modified silane coupling agent was not evenly dispersed during the reaction with Nylon-66, which led to a decrease in the fireproof insulation and tensile properties of the final fireproof insulation material.

[0041] (3) Comparative Example 2 shows that the test results of the fireproof insulation material modified by the present invention are generally lower than those of the corresponding Examples 1 to 4. This may be because the addition of too little silane coupling agent suspension in Comparative Example 2 resulted in a low degree of crosslinking of the crosslinked network structure when the silane coupling agent formed covalent bonds with nylon-66 through hydrolysis and condensation. This led to a decrease in the fireproof insulation and tensile properties of the final fireproof insulation material.

[0042] (4) Comparative Example 3 shows that the fireproof insulation material modified by the present invention is generally lower than that of corresponding Examples 1 to 4. This may be because the addition of high content of nano silica in Comparative Example 3 will form a dense rigid particle network in nylon-66, which physically blocks the nylon-66 molecular chains from getting close to each other. At the same time, the hydroxyl groups on the surface of nano silica will react with the silane coupling agent. This reaction consumes the silane coupling agent that should react with nylon-66, reduces the effective crosslinking density, and thus reduces the fireproof insulation and tensile properties of the final fireproof insulation material.

[0043] (5) Comparative Example 4 shows that the test results of the fireproof insulation material modified by the present invention are generally lower than those of corresponding Examples 1 to 4. This may be because Comparative Example 4 added too little nano silica. The specific surface area of ​​nano silica determines its maximum adsorption capacity. Adding too little nano silica cannot adsorb more silane coupling agent, so the excess silane coupling agent is free in the system and cannot form a dense network cross-linking structure with nylon-66, which in turn reduces the fireproof insulation and tensile properties of the final fireproof insulation material.

[0044] The embodiments described above provide a detailed explanation of the technical solutions and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Various changes and modifications can be made to the present invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed.

Claims

1. The production of a novel fire-resistant and insulating material for new energy batteries, characterized in that, The production process includes the following steps: Pretreated PA particles are obtained by heating them to 80°C and drying them for 4 hours. Pretreated PA, modified silane coupling agent, dicumyl peroxide and antioxidant 1010 are melt-blended in a weight ratio of 100:1.5:0.3:0.4, and then granulated, injection molded and irradiated to obtain a fireproof and insulating material.

2. The production method of a novel fireproof and insulating material for new energy batteries according to claim 1, characterized in that, The preparation method of the modified silane coupling agent includes the following steps: A modified silane coupling agent is obtained by mixing and reacting a silane coupling agent suspension and nano-silica at a weight ratio of 0.3~0.5:

1.

3. The production method of a novel fireproof and insulating material for new energy batteries according to claim 2, characterized in that, The preparation method of the silane coupling agent suspension includes the following steps: A silane coupling agent, deionized water, and anhydrous ethanol were mixed in a weight ratio of 1:0.1 to 0.2:1, the pH was adjusted to 4, and the mixture was heated to 40°C for 3 hours to obtain a silane coupling agent suspension.

4. The production method of a novel fireproof and insulating material for new energy batteries according to claim 3, characterized in that, The silane coupling agent includes vinyltrimethoxysilane.

5. The production method of a novel fireproof and insulating material for new energy batteries according to claim 2, characterized in that, The particle size of the nano-silica is 30 nm.

6. The production of a novel fireproof and insulating material for new energy batteries according to claim 1, characterized in that, The conditions for melt blending include a temperature of 260°C, a time of 10 min, and a rotation speed of 80 r / min.

7. The production of a novel fire-resistant and insulating material for new energy batteries according to claim 1, characterized in that, The granulation conditions include a particle size of 2 mm.

8. The production of a novel fireproof and insulating material for new energy batteries according to claim 1, characterized in that, The injection molding conditions include a holding pressure of 90 MPa, a holding time of 10 s, and an injection temperature of 270°C.

9. The production of a novel fireproof and insulating material for new energy batteries according to claim 1, characterized in that, The conditions for the irradiation modification include an irradiation energy of 150 keV, an irradiation dose of 100 kGy, and an irradiation time of 20 s.

10. The application of a fireproof insulation material obtained by producing a novel fireproof insulation material for new energy batteries according to any one of claims 1 to 9 in the field of battery fireproof insulation.

Images