CN116247338B - Integrated heating film of battery structure - Google Patents
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/60—Heating or cooling; Temperature control
- H01M10/65—Means for temperature control structurally associated with the cells
- H01M10/653—Means for temperature control structurally associated with the cells characterised by electrically insulating or thermally conductive materials
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
The invention relates to the field of battery heating films, in particular to an integrated heating film of a battery structural member, which is arranged in the battery structural member, and comprises two insulating heat conducting layers and heating components arranged between the two insulating heat conducting layers, wherein the heating components are metal heating conductors capable of being electrified, and the two insulating heat conducting layers are made of the same material and are both modified polyimide materials; the modified polyimide material is synthesized by taking 4,4' -diaminodiphenyl ether and pyromellitic dianhydride as reactants and taking diamino-amido-molybdenum nitride powder as a heat conducting material. The battery heating film designed by the invention has the greatest advantages over the conventional heating film on the market that the battery heating film designed by the invention has better material property and better heat conductivity, and is more suitable for being used as the battery heating film.
Description
Technical Field
The invention relates to the field of battery heating films, in particular to an integrated heating film for a battery structural part.
Background
With the great development of the automobile industry and the enhancement of environmental protection consciousness, new energy electric automobiles are increasingly favored. The electric automobile not only can reduce the emission of polluted gas, but also can effectively reduce the dependence on petroleum resources. For an electric automobile, a battery is a power source of the electric automobile, and in a low-temperature natural environment (for example, at-20 ℃), a lithium ion power battery has 2 layers of problems, and one problem is that the charging and discharging capacities of a rechargeable battery are deviated at a low temperature, and even in a full grid condition, the pushing capacity of the automobile is greatly affected; another problem is that low temperature battery charging has long been known to be a faster way of losing service life of the power battery. At low temperature, the internal structure of the rechargeable battery has poor transmission capability of electrified positive ions, and the migration and placement capability of positive charges in the internal structure of the battery anode material structure are also poor. If the low-temperature normal current amount battery is charged, a plurality of lithium ions are deposited on the negative-stage surface and are not placed in the battery, and after electronic devices are obtained in various modes, the lithium ions are accumulated on the electrode surface to generate lithium compound deposition; the lithium metal material is easy to generate the condition of uneven crystal growth and development, cementite grows and develops to a sufficient operation scale, and then the cementite is likely to poke through the diaphragm, so that the positive and negative middle is immediately communicated to generate internal short circuit fault. Therefore, in order to solve the above-described problems, it is necessary to configure a battery heating system for heating the battery.
Heating using a heating film is a common heating mode of a battery heating system, but as the requirement for the heating speed of the battery system increases, the power of the heating film is also higher and higher. The surface temperature of a heating film of a battery in the current market can reach about 200 ℃ after long-time power on, and the performance of the heating film can be reduced and damaged under the long-time high-temperature condition, so that the risk of thermal runaway of the battery is caused; in addition, the heat conduction efficiency of the heating film is poor at present, so that the heating process is slower, and heat is accumulated on the heating film layer and cannot be transferred to the battery as soon as possible. Therefore, there is a need for a battery heating film that is resistant to high temperatures and has good thermal conductivity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a battery structural member integrated heating film which is high-temperature resistant and good in heat conductivity.
The aim of the invention is realized by adopting the following technical scheme:
the integrated heating film of the battery structural part is arranged in the battery structural part, wherein the heating film comprises two layers of insulating heat conduction layers and heating components arranged between the two layers of insulating heat conduction layers, the heating components are metal heating conductors capable of being electrified, and the two layers of insulating heat conduction layers are made of the same material and are all modified polyimide materials.
Preferably, the metal heating conductor is a curved metal wire or metal foil; the voltage is 1.5V-380V.
Preferably, the modified polyimide material is synthesized by taking 4,4' -diaminodiphenyl ether and pyromellitic dianhydride as reactants and taking diamino-amido-molybdenum nitride powder as a heat conducting material.
Preferably, the thickness of each insulating heat conducting layer is 0.5-1mm; the thickness of the metal heat-generating conductor is 50-100 μm.
Preferably, the specific activation steps of the activated molybdenum nitride powder are as follows:
mixing molybdenum nitride powder in ethanol solution, adding an aminosilane coupling agent, stirring for 3-8h at room temperature, filtering to collect powder, washing with deionized water for at least three times, and drying to obtain activated molybdenum nitride powder;
wherein the particle size of the molybdenum nitride powder is 200-300nm, the mass fraction of the ethanol solution is 35% -55%, and the mass ratio of the molybdenum nitride powder, the aminosilane coupling agent and the ethanol solution is 1.1-1.5:0.1-0.6:10-20.
Preferably, the preparation process of the diamino-amido-molybdenum nitride powder comprises the following steps:
s1, weighing ethyl trifluoroacetate, mixing with diethyl ether, uniformly stirring in an ice-water bath, adding 3, 5-diaminobenzoic acid, continuously stirring in the ice-water bath, removing a solvent, and purifying to obtain a trifluoroacetyl-carboxyl pyrimidine compound; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the ethyl trifluoroacetate to the diethyl ether is 0.27-0.34:0.01-0.03:10-20;
s2, weighing a trifluoroacetyl-carboxyl pyrimidine compound, N-dimethylformamide and thionyl chloride, adding the trifluoroacetyl-carboxyl pyrimidine compound, the N, N-dimethylformamide and the thionyl chloride into a reaction flask, and fully mixing to form a solution A; wherein the mass ratio of the trifluoroacetyl-carboxyl pyrimidine compound to the thionyl chloride is 0.42-0.58:3-5; the mass ratio of the N, N-dimethylformamide to the trifluoroacetyl-carboxypyrimidine compound is 0.01-0.03:1;
s3, placing the reaction flask containing the solution A in a magnetic stirring oil bath, heating the oil bath to 70-80 ℃, carrying out reflux stirring reaction for 3-5h, naturally cooling to room temperature, then removing the solvent by rotary evaporation, and dissolving the obtained product in dichloromethane with the mass of 5 times to obtain a solution B;
s4, weighing activated molybdenum nitride powder, triethylamine and dichloromethane, adding the activated molybdenum nitride powder, the triethylamine and the dichloromethane into a beaker, and fully mixing to form a solution C; wherein the mass ratio of the activated molybdenum nitride powder to the triethylamine to the dichloromethane is 1-2:0.3-0.6:10;
s5, gradually dropwise adding the solution B from room temperature to 5 ℃, controlling the temperature of the mixed solution to be between 15 and 20 ℃, continuously stirring for 1 to 3 hours after all dropwise adding, stopping stirring, standing for precipitation, filtering the liquid, washing the residual solid, and drying under reduced pressure to obtain trifluoroacetyl-amido-molybdenum nitride powder; wherein the mass ratio of the solution B to the solution C is 1:3-5.
S6, mixing trifluoroacetyl-amido-molybdenum nitride powder with a methanol solution, uniformly stirring at room temperature, dropwise adding a sodium carbonate solution with the mass concentration of 5%, stirring for 4-6 hours, removing a solvent, sequentially washing with deionized water and a saturated sodium chloride solution for at least three times, and drying under vacuum to obtain diamino-amido-molybdenum nitride powder; wherein the formaldehyde solution is obtained by mixing formaldehyde and deionized water according to a mass ratio of 1:2, and the mass ratio of trifluoroacetyl-amido-molybdenum nitride powder, methanol solution and sodium carbonate solution is 0.5-1:10-20:3-5.
Preferably, the synthesis process of the modified polyimide material comprises the following steps:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at a speed of 150-250rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution;
(2) Adding diamino-amido-molybdenum nitride powder into the polyamic acid reaction liquid, simultaneously increasing the stirring speed to 400-600rpm, and continuously stirring at room temperature for 50-100min to obtain a modified reaction liquid;
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 150-250rpm for 10-20min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die in an oven for treatment to obtain the modified polyimide material.
Preferably, in the step (1), the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 1.8-2.2:1.96-2.4:5-10.
Preferably, in the step (2), the mass ratio of the diamino-amido-molybdenum nitride powder to the polyamic acid reaction solution is 1.5-3:20-40.
Preferably, in the step (3), the mass ratio of the triethylamine, the acetic anhydride and the modification reaction liquid is 0.5-1:0.5-1:2-4.
Preferably, in the step (3), the in-oven treatment is divided into two processes which are sequentially performed: the first process is to treat at 110-135 deg.c for 2-4 hr; the second process is to treat at 300-350 deg.c for 4-8 hr.
The beneficial effects of the invention are as follows:
1. the invention provides an integrated heating film for a battery structural part, which comprises two insulating heat conducting layers and a heating element. The heating element is an electrified metal heating conductor, and the purpose of the heating element is to convert electric energy into heat energy; the insulating heat conducting layer plays roles of heat conduction and insulation. The battery heating film designed by the invention has the greatest advantages over the conventional heating film on the market that the battery heating film designed by the invention has higher material property and performance and better heat conductivity, so that the battery heating film is more suitable for being used as the battery heating film.
2. The insulating heat conducting layer of the battery heating film prepared by the invention is made of modified polyimide material, and is obtained by improvement on the basis of the traditional polyimide material. The improved process mainly comprises the following steps: the self-made diamino-amido-molybdenum nitride powder is used as a heat conducting material, and the diamino can participate in the synthesis process of the polyimide material, so that the effect of crosslinking modification is achieved, and meanwhile, the heat conducting effect is also achieved. Compared with the traditional polyimide, the polyimide material after improvement has better improvement in physical property and heat conduction property.
3. In the process of synthesizing the modified polyimide material, the modifier diamino-amido-molybdenum nitride powder is a product obtained by reacting 3, 5-diaminobenzoic acid which is a compound containing both diamino and carboxyl with activated molybdenum nitride powder containing amino. The reaction aims to crosslink and combine carboxyl groups on 3, 5-diaminobenzoic acid and amino groups on activated molybdenum nitride powder to generate amide groups, so as to obtain the heat-conducting material containing both diamino and amide groups. In order to prevent the loss of amino, the amino is protected by using a trifluoroacetyl mode, and finally the trifluoroacetyl of the protecting group is removed in an alkaline aqueous solution of methanol to obtain the amino.
4. Compared with the conventional heat conducting material, the molybdenum nitride heat conducting material treated by the method can have better compatibility with the modified polyimide material, and the heat conductivity and durability of the modified polyimide material are enhanced.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The invention is further described with reference to the following examples.
Example 1
The integrated heating film of the battery structural part is arranged in the battery structural part, wherein the heating film comprises two insulating heat conducting layers and a heating element arranged between the two insulating heat conducting layers, the heating element is a metal heating conductor capable of being electrified, and the metal heating conductor is a curved metal wire or metal foil; the two insulating heat conducting layers are the same in material and are both modified polyimide materials; wherein, the thickness of each insulating heat conducting layer is 0.6mm; the thickness of the metal heat-generating conductor was 80. Mu.m.
In the above, the synthesis process of the modified polyimide material comprises:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at 200rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 2:2.12:7.
(2) Adding diamino-amido-molybdenum nitride powder into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 500rpm, and continuously stirring at room temperature for 80min to obtain a modified reaction solution; wherein the mass ratio of the diamino-amido-molybdenum nitride powder to the polyamic acid reaction liquid is 2.2:30.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 200rpm for 15min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat for 3 hours at 125 ℃; the second process is to treat for 6 hours at 300 ℃, then cool to room temperature, finally obtain the modified polyimide material; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 0.8:0.6:3.
Wherein, the preparation process of the bisamino-amido-molybdenum nitride powder added in the step (2) comprises the following steps:
s1, weighing ethyl trifluoroacetate, mixing with diethyl ether, uniformly stirring in an ice-water bath, adding 3, 5-diaminobenzoic acid, continuously stirring in the ice-water bath, removing a solvent, and purifying to obtain a trifluoroacetyl-carboxyl pyrimidine compound; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the ethyl trifluoroacetate to the diethyl ether is 0.3:0.02:15;
s2, weighing a trifluoroacetyl-carboxyl pyrimidine compound, N-dimethylformamide and thionyl chloride, adding the trifluoroacetyl-carboxyl pyrimidine compound, the N, N-dimethylformamide and the thionyl chloride into a reaction flask, and fully mixing to form a solution A; wherein, the mass ratio of the trifluoroacetyl-carboxyl pyrimidine compound to the thionyl chloride is 0.5:4; the mass ratio of the N, N-dimethylformamide to the trifluoroacetyl-carboxypyrimidine compound is 0.02:1;
s3, placing the reaction flask containing the solution A in a magnetic stirring oil bath, heating the oil bath to 75 ℃, refluxing and stirring for reaction for 4 hours, naturally cooling to room temperature, removing the solvent by rotary evaporation, and dissolving the obtained product in dichloromethane with the mass of 5 times to obtain a solution B;
s4, weighing activated molybdenum nitride powder, triethylamine and dichloromethane, adding the activated molybdenum nitride powder, the triethylamine and the dichloromethane into a beaker, and fully mixing to form a solution C; wherein the mass ratio of the activated molybdenum nitride powder to the triethylamine to the dichloromethane is 1.5:04:10;
s5, gradually dropwise adding the solution B from room temperature to 5 ℃, controlling the temperature of the mixed solution to be between 15 and 20 ℃, continuously stirring for 2 hours after all dropwise adding, stopping stirring, standing for precipitation, filtering the liquid, washing the rest solid, and drying under reduced pressure to obtain trifluoroacetyl-amido-molybdenum nitride powder; wherein the mass ratio of the solution B to the solution C is 1:4.
S6, mixing trifluoroacetyl-amido-molybdenum nitride powder with a methanol solution, uniformly stirring at room temperature, dropwise adding a sodium carbonate solution with the mass concentration of 5%, stirring for 5 hours, removing a solvent, sequentially washing with deionized water and a saturated sodium chloride solution for at least three times, and drying under vacuum to obtain diamino-amido-molybdenum nitride powder; wherein the formaldehyde solution is obtained by mixing formaldehyde and deionized water according to a mass ratio of 1:2, and the mass ratio of trifluoroacetyl-amido-molybdenum nitride powder, methanol solution and sodium carbonate solution is 0.7:15:4.
Example 2
The integrated heating film of the battery structural part is arranged in the battery structural part, wherein the heating film comprises two insulating heat conducting layers and a heating element arranged between the two insulating heat conducting layers, the heating element is a metal heating conductor capable of being electrified, and the metal heating conductor is a curved metal wire or metal foil; the two insulating heat conducting layers are the same in material and are both modified polyimide materials; wherein, the thickness of each insulating heat conducting layer is 0.5mm; the thickness of the metal heat-generating conductor was 50. Mu.m.
In the above, the synthesis process of the modified polyimide material comprises:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at 150rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 1.8:1.96:5.
(2) Adding diamino-amido-molybdenum nitride powder into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 400rpm, and continuously stirring at room temperature for 50min to obtain a modified reaction solution; wherein the mass ratio of the diamino-amido-molybdenum nitride powder to the polyamic acid reaction liquid is 1.5:20.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 150rpm for 10min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat at 110 ℃ for 2 hours; the second process is to treat for 4 hours at 300 ℃, then cool to room temperature, finally obtain the modified polyimide material; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 0.5:0.5:2.
Wherein, the preparation process of the bisamino-amido-molybdenum nitride powder added in the step (2) comprises the following steps:
s1, weighing ethyl trifluoroacetate, mixing with diethyl ether, uniformly stirring in an ice-water bath, adding 3, 5-diaminobenzoic acid, continuously stirring in the ice-water bath, removing a solvent, and purifying to obtain a trifluoroacetyl-carboxyl pyrimidine compound; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the ethyl trifluoroacetate to the diethyl ether is 0.27:0.01:10;
s2, weighing a trifluoroacetyl-carboxyl pyrimidine compound, N-dimethylformamide and thionyl chloride, adding the trifluoroacetyl-carboxyl pyrimidine compound, the N, N-dimethylformamide and the thionyl chloride into a reaction flask, and fully mixing to form a solution A; wherein the mass ratio of the trifluoroacetyl-carboxyl pyrimidine compound to the thionyl chloride is 0.42:3; the mass ratio of the N, N-dimethylformamide to the trifluoroacetyl-carboxypyrimidine compound is 0.01:1;
s3, placing the reaction flask containing the solution A in a magnetic stirring oil bath, heating the oil bath to 70 ℃, refluxing and stirring for reaction for 3 hours, naturally cooling to room temperature, removing the solvent by rotary evaporation, and dissolving the obtained product in dichloromethane with the mass of 5 times to obtain a solution B;
s4, weighing activated molybdenum nitride powder, triethylamine and dichloromethane, adding the activated molybdenum nitride powder, the triethylamine and the dichloromethane into a beaker, and fully mixing to form a solution C; wherein the mass ratio of the activated molybdenum nitride powder to the triethylamine to the dichloromethane is 1:0.3:10;
s5, gradually dropwise adding the solution B from room temperature to 5 ℃, controlling the temperature of the mixed solution to be between 15 and 20 ℃, continuously stirring for 1h after all dropwise adding, stopping stirring, standing for precipitation, filtering the liquid, washing the rest solid, and drying under reduced pressure to obtain trifluoroacetyl-amido-molybdenum nitride powder; wherein the mass ratio of the solution B to the solution C is 1:3.
S6, mixing trifluoroacetyl-amido-molybdenum nitride powder with a methanol solution, uniformly stirring at room temperature, dropwise adding a sodium carbonate solution with the mass concentration of 5%, stirring for 4 hours, removing a solvent, sequentially washing with deionized water and a saturated sodium chloride solution for at least three times, and drying under vacuum to obtain diamino-amido-molybdenum nitride powder; wherein the formaldehyde solution is obtained by mixing formaldehyde and deionized water according to a mass ratio of 1:2, and the mass ratio of trifluoroacetyl-amido-molybdenum nitride powder, methanol solution and sodium carbonate solution is 0.5:10:3.
Example 3
The integrated heating film of the battery structural part is arranged in the battery structural part, wherein the heating film comprises two insulating heat conducting layers and a heating element arranged between the two insulating heat conducting layers, the heating element is a metal heating conductor capable of being electrified, and the metal heating conductor is a curved metal wire or metal foil; the two insulating heat conducting layers are the same in material and are both modified polyimide materials; wherein, the thickness of each insulating heat conducting layer is 0.6mm; the thickness of the metal heat-generating conductor was 80. Mu.m.
In the above, the synthesis process of the modified polyimide material comprises:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at the speed of 250rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 2.2:2.4:10.
(2) Adding diamino-amido-molybdenum nitride powder into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 600rpm, and continuously stirring at room temperature for 100min to obtain a modified reaction solution; wherein the mass ratio of the diamino-amido-molybdenum nitride powder to the polyamic acid reaction liquid is 3:40.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 250rpm for 20min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat at 135 ℃ for 4 hours; the second process is that the modified polyimide material is obtained after the treatment for 8 hours at 350 ℃ and then cooled to room temperature; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 1:1:4.
Wherein, the preparation process of the bisamino-amido-molybdenum nitride powder added in the step (2) comprises the following steps:
s1, weighing ethyl trifluoroacetate, mixing with diethyl ether, uniformly stirring in an ice-water bath, adding 3, 5-diaminobenzoic acid, continuously stirring in the ice-water bath, removing a solvent, and purifying to obtain a trifluoroacetyl-carboxyl pyrimidine compound; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the ethyl trifluoroacetate to the diethyl ether is 0.34:0.03:20;
s2, weighing a trifluoroacetyl-carboxyl pyrimidine compound, N-dimethylformamide and thionyl chloride, adding the trifluoroacetyl-carboxyl pyrimidine compound, the N, N-dimethylformamide and the thionyl chloride into a reaction flask, and fully mixing to form a solution A; wherein, the mass ratio of the trifluoroacetyl-carboxyl pyrimidine compound to the thionyl chloride is 0.58:5; the mass ratio of the N, N-dimethylformamide to the trifluoroacetyl-carboxypyrimidine compound is 0.03:1;
s3, placing the reaction flask containing the solution A in a magnetic stirring oil bath pot, heating the oil bath pot to 80 ℃, refluxing, stirring and reacting for 5 hours, naturally cooling to room temperature, removing the solvent by rotary evaporation, and dissolving the obtained product in dichloromethane with the mass of 5 times to obtain a solution B;
s4, weighing activated molybdenum nitride powder, triethylamine and dichloromethane, adding the activated molybdenum nitride powder, the triethylamine and the dichloromethane into a beaker, and fully mixing to form a solution C; wherein the mass ratio of the activated molybdenum nitride powder to the triethylamine to the dichloromethane is 2:0.6:10;
s5, gradually dropwise adding the solution B from room temperature to 5 ℃, controlling the temperature of the mixed solution to be between 15 and 20 ℃, continuously stirring for 3 hours after all dropwise adding, stopping stirring, standing for precipitation, filtering the liquid, washing the rest solid, and drying under reduced pressure to obtain trifluoroacetyl-amido-molybdenum nitride powder; wherein the mass ratio of the solution B to the solution C is 1:5.
S6, mixing trifluoroacetyl-amido-molybdenum nitride powder with a methanol solution, uniformly stirring at room temperature, dropwise adding a sodium carbonate solution with the mass concentration of 5%, stirring for 6 hours, removing a solvent, sequentially washing with deionized water and a saturated sodium chloride solution for at least three times, and drying under vacuum to obtain diamino-amido-molybdenum nitride powder; the formaldehyde solution is obtained by mixing formaldehyde and deionized water according to a mass ratio of 1:2, and the mass ratio of trifluoroacetyl-amido-molybdenum nitride powder, methanol solution and sodium carbonate solution is 1:20:5.
Comparative example 1
A modified polyimide material is different from the embodiment 1 in that 4,4' -diaminodiphenyl ether and pyromellitic dianhydride are used as reactants, a heat conducting material is activated molybdenum nitride powder, and the preparation process of the heat conducting material is the same as that of the embodiment 1.
Specific syntheses of the modified polyimide materials in this comparative example include:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at 200rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 2:2.12:7.
(2) Adding activated molybdenum nitride powder into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 500rpm, and continuously stirring at room temperature for 80min to obtain a modified reaction solution; wherein the mass ratio of the activated molybdenum nitride powder to the polyamic acid reaction liquid is 2.2:30.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 200rpm for 15min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat for 3 hours at 125 ℃; the second process is to treat for 6 hours at 300 ℃, then cool to room temperature, finally obtain the modified polyimide material; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 0.8:0.6:3.
Comparative example 2
A modified polyimide material was prepared by using 4,4' -diaminodiphenyl ether and pyromellitic dianhydride as reactants and a mixture of 3, 5-diaminobenzoic acid and activated molybdenum nitride powder as additives, differing from example 1; the mass ratio of the 3, 5-diaminobenzoic acid to the activated molybdenum nitride powder in the mixture of the 3, 5-diaminobenzoic acid and the activated molybdenum nitride powder is 1:20.
Specific syntheses of the modified polyimide materials in this comparative example include:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at 200rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 2:2.12:7.
(2) Adding a mixture of 3, 5-diaminobenzoic acid and activated molybdenum nitride powder into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 500rpm, and continuously stirring at room temperature for 80min to obtain a modified reaction solution; wherein the mass ratio of the mixture to the polyamic acid reaction liquid is 2.2:30.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 200rpm for 15min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat for 3 hours at 125 ℃; the second process is to treat for 6 hours at 300 ℃, then cool to room temperature, finally obtain the modified polyimide material; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 0.8:0.6:3.
Comparative example 3
A modified polyimide material was prepared by using 4,4' -diaminodiphenyl ether and pyromellitic dianhydride as reactants and 3, 5-diaminobenzoic acid as an additive, as compared with example 1, and the addition amount of 3, 5-diaminobenzoic acid was calculated by conversion with the ratio of example 1.
Specific syntheses of the modified polyimide materials in this comparative example include:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at 200rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution; wherein the mass ratio of the 4,4' -diaminodiphenyl ether, pyromellitic dianhydride and the N-methylpyrrolidone is 2:2.12:7.
(2) Adding 3, 5-diaminobenzoic acid into the polyamic acid reaction solution, simultaneously increasing the stirring speed to 500rpm, and continuously stirring at room temperature for 80min to obtain a modified reaction solution; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the polyamic acid reaction solution is 0.11:30.
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 200rpm for 15min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die into an oven for treatment, wherein the steps comprise the following steps of: the first process is to treat for 3 hours at 125 ℃; the second process is to treat for 6 hours at 300 ℃, then cool to room temperature, finally obtain the modified polyimide material; wherein the mass ratio of the triethylamine to the acetic anhydride to the modification reaction liquid is 0.8:0.6:3.
In the examples of the present invention, represented by example 1, the properties were evaluated in the same manner as in the modified polyimide materials obtained in comparative examples 1, 2 and 3, bending strength GB/T1449, compressive strength GB/T1448, unnotched impact strength test standard GB/T1043, and the results are summarized in Table 1.
TABLE 1 Performance of different modified polyimide materials
As can be seen from Table 1, the modified polyimide material prepared in example 1 of the present invention has better performances in terms of flexural strength, compressive strength, unnotched impact strength, heat distortion temperature than the other comparative examples, and in addition, the thermal conductivity can reach 1.25W/(mK), which is far higher than the performances of the other comparative examples. Comparative example 2 and comparative example 3 are inferior in mechanical properties and heat distortion temperature to comparative example 2 in that only the bis-amino compound 3, 5-diaminobenzoic acid is added as a modifier, and the heat conductivity is insufficient because no heat conductive material is added; while comparative example 1 and comparative example 2 are slightly weaker in each property than comparative example 2, it is shown that the addition of 3, 5-diaminobenzoic acid improves the polyimide material to some extent, but the improvement is not great.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The integrated heating film of the battery structural part is arranged in the battery structural part and is characterized by comprising two insulating heat conducting layers and heating components arranged between the two insulating heat conducting layers, wherein the heating components are metal heating conductors capable of being electrified, and the two insulating heat conducting layers are made of the same material and are both modified polyimide materials;
the modified polyimide material is synthesized by taking 4,4' -diaminodiphenyl ether and pyromellitic dianhydride as reactants and taking diamino-amido-molybdenum nitride powder as a heat conducting material;
the preparation process of the diamino-amido-molybdenum nitride powder comprises the following steps:
s1, weighing ethyl trifluoroacetate, mixing with diethyl ether, uniformly stirring in an ice-water bath, adding 3, 5-diaminobenzoic acid, continuously stirring in the ice-water bath, removing a solvent, and purifying to obtain a trifluoroacetyl-carboxyl pyrimidine compound; wherein the mass ratio of the 3, 5-diaminobenzoic acid to the ethyl trifluoroacetate to the diethyl ether is 0.27-0.34:0.01-0.03:10-20;
s2, weighing a trifluoroacetyl-carboxyl pyrimidine compound, N-dimethylformamide and thionyl chloride, adding the trifluoroacetyl-carboxyl pyrimidine compound, the N, N-dimethylformamide and the thionyl chloride into a reaction flask, and fully mixing to form a solution A; wherein the mass ratio of the trifluoroacetyl-carboxyl pyrimidine compound to the thionyl chloride is 0.42-0.58:3-5; the mass ratio of the N, N-dimethylformamide to the trifluoroacetyl-carboxypyrimidine compound is 0.01-0.03:1;
s3, placing the reaction flask containing the solution A in a magnetic stirring oil bath, heating the oil bath to 70-80 ℃, carrying out reflux stirring reaction for 3-5h, naturally cooling to room temperature, then removing the solvent by rotary evaporation, and dissolving the obtained product in dichloromethane with the mass of 5 times to obtain a solution B;
s4, weighing activated molybdenum nitride powder, triethylamine and dichloromethane, adding the activated molybdenum nitride powder, the triethylamine and the dichloromethane into a beaker, and fully mixing to form a solution C; wherein the mass ratio of the activated molybdenum nitride powder to the triethylamine to the dichloromethane is 1-2:0.3-0.6:10;
s5, gradually dropwise adding the solution B from room temperature to 5 ℃, controlling the temperature of the mixed solution to be between 15 and 20 ℃, continuously stirring for 1 to 3 hours after all dropwise adding, stopping stirring, standing for precipitation, filtering the liquid, washing the residual solid, and drying under reduced pressure to obtain trifluoroacetyl-amido-molybdenum nitride powder; wherein the mass ratio of the solution B to the solution C is 1:3-5;
s6, mixing trifluoroacetyl-amido-molybdenum nitride powder with a methanol solution, uniformly stirring at room temperature, dropwise adding a sodium carbonate solution with the mass concentration of 5%, stirring for 4-6 hours, removing a solvent, sequentially washing with deionized water and a saturated sodium chloride solution for at least three times, and drying under vacuum to obtain diamino-amido-molybdenum nitride powder; wherein the formaldehyde solution is obtained by mixing formaldehyde and deionized water according to a mass ratio of 1:2, and the mass ratio of trifluoroacetyl-amido-molybdenum nitride powder, methanol solution and sodium carbonate solution is 0.5-1:10-20:3-5;
the specific activation steps of the activated molybdenum nitride powder are as follows:
mixing molybdenum nitride powder in ethanol solution, adding an aminosilane coupling agent, stirring for 3-8h at room temperature, filtering to collect powder, washing with deionized water for at least three times, and drying to obtain activated molybdenum nitride powder;
wherein the particle size of the molybdenum nitride powder is 200-300nm, the mass fraction of the ethanol solution is 35% -55%, and the mass ratio of the molybdenum nitride powder, the aminosilane coupling agent and the ethanol solution is 1.1-1.5:0.1-0.6:10-20.
2. The integrated heating film for a battery structural member according to claim 1, wherein the metal heat-generating conductor is a curved wire or foil; the voltage is 1.5V-380V.
3. The integrated heating film for a battery structural member of claim 1, wherein the thickness of each of said insulating and thermally conductive layers is 0.1-0.3mm; the thickness of the metal heat-generating conductor is 10-50 μm.
4. The integrated heating film for a battery structural member according to claim 1, wherein the synthesis process of the modified polyimide material comprises:
(1) Weighing 4,4' -diaminodiphenyl ether, dissolving in N-methylpyrrolidone, gradually adding pyromellitic dianhydride, stirring at a speed of 150-250rpm while adding, and continuously stirring at room temperature until the reaction solution becomes clear to form polyamic acid reaction solution;
(2) Adding diamino-amido-molybdenum nitride powder into the polyamic acid reaction liquid, simultaneously increasing the stirring speed to 400-600rpm, and continuously stirring at room temperature for 50-100min to obtain a modified reaction liquid;
(3) Sequentially adding a catalyst triethylamine and a dehydrating agent acetic anhydride into the modified reaction liquid, stirring at a speed of 150-250rpm for 10-20min, defoaming, casting the reaction liquid onto a die, performing gel aging treatment for at least 24h, and then placing the die in an oven for treatment to obtain the modified polyimide material.
5. The integrated heating film for a battery structural member according to claim 4, wherein in the step (1), the mass ratio of 4,4' -diaminodiphenyl ether, pyromellitic dianhydride to N-methylpyrrolidone is 1.8-2.2:1.96-2.4:5-10.
6. The integrated heating film for a battery structural member according to claim 4, wherein in the step (2), the mass ratio of the bisamino-amido-molybdenum nitride powder to the polyamic acid reaction solution is 1.5-3:20-40.
7. The integrated heating film for a battery structural member according to claim 6, wherein in the step (3), the mass ratio of triethylamine, acetic anhydride to the modifying reaction liquid is 0.5-1:0.5-1:2-4.
8. The integrated heating film for a battery structural member according to claim 4, wherein in the step (3), the in-oven treatment is divided into two processes which are sequentially performed: the first process is to treat at 110-135 deg.c for 2-4 hr; the second process is to treat at 300-350 deg.c for 4-8 hr.
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| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN114644815A (en) * | 2022-03-30 | 2022-06-21 | 福建腾博新材料科技有限公司 | Lithium battery insulating film for new energy automobile and preparation method thereof |
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| JP2009191161A (en) * | 2008-02-14 | 2009-08-27 | Toyobo Co Ltd | Polyimide film |
| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN114644815A (en) * | 2022-03-30 | 2022-06-21 | 福建腾博新材料科技有限公司 | Lithium battery insulating film for new energy automobile and preparation method thereof |
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