CN116742205B - Safety heating film capable of absorbing expansion of battery without waste discharge - Google Patents

Safety heating film capable of absorbing expansion of battery without waste discharge Download PDF

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Publication number
CN116742205B
CN116742205B CN202310872136.0A CN202310872136A CN116742205B CN 116742205 B CN116742205 B CN 116742205B CN 202310872136 A CN202310872136 A CN 202310872136A CN 116742205 B CN116742205 B CN 116742205B
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polybenzimidazole
graphene conductive
vinyl
battery
heating film
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CN116742205A (en
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吴金鹏
蒋小勇
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Guangdong Zhongyu Hengtong Thermal Technology Co ltd
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Guangdong Zhongyu Hengtong Thermal Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/615—Heating or keeping warm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/617—Types of temperature control for achieving uniformity or desired distribution of temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/62—Heating or cooling; Temperature control specially adapted for specific applications
    • H01M10/625—Vehicles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/65—Means for temperature control structurally associated with the cells
    • H01M10/657—Means for temperature control structurally associated with the cells by electric or electromagnetic means
    • H01M10/6571—Resistive heaters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/233—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions
    • H01M50/242—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders characterised by physical properties of casings or racks, e.g. dimensions adapted for protecting batteries against vibrations, collision impact or swelling
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/02—Details
    • H05B3/03—Electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/145—Carbon only, e.g. carbon black, graphite
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/20—Inorganic coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a waste discharge-free safe heating film capable of absorbing battery expansion, which comprises a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first protective layer and the second protective layer are made of the same material and are both modified polybenzimidazole materials. The protective layer of the safe heating film is prepared from a special modified polybenzimidazole material, has higher strength and toughness, and can absorb the expansion of a battery to ensure the use safety of the battery; in addition, the safe heating film uses the graphene conductive layer to replace alloy materials in the market, so that the defect that the manufacturing of an alloy heating body is harmful to the environment is overcome, and the heating is more uniform.

Description

Safety heating film capable of absorbing expansion of battery without waste discharge
Technical Field
The invention relates to the field of batteries, in particular to a safe heating film capable of absorbing battery expansion without waste discharge.
Background
Power cells are widely used in various vehicles such as automobiles, unmanned aerial vehicles, and electronic devices. The characteristic that the charging and discharging performance of the power battery is greatly reduced in a low-temperature environment greatly influences the winter endurance mileage of the electric automobile, restricts the northern market of the electric automobile, is a great technical defect in the development process of the full-weather electric automobile, and is high Wen Youhui, so that the performance of the lithium battery is irreversibly attenuated, and even potential safety hazards are caused.
The battery heating film is a material for heat preservation and heating, and can be generally used in the fields of battery module heating and heat preservation, electric automobile suspension, hanging heating and heat preservation and the like. The pressure-sensitive adhesive sheet has heat conduction and heat insulation properties, and can convert electric energy into heat energy for heating, so that the object is heated and kept warm. The basic principle of the battery heating film is to utilize the current impedance and resistance heating principle of the material to achieve the effect of rapid heating. The PTC heating body is adopted in the inner part of the heating device, so that high-load heating can be realized, and the heating device is very safe and reliable.
The conventional product for heating the power battery pack is generally an alloy heating film, and the manufacturing method of the heating product generally adopts a method of etching an alloy material by a wet method to form a heating body, and then the heating body is packaged between two layers of insulating films. The alloy heating film mainly has the following problems: firstly, the volume expansion of the battery can be generated in the use process, and the alloy heating materials in the current market are harder, so that the expansion of the battery can not be absorbed to cause the extrusion damage; secondly, the heat conduction efficiency of the insulating film of the alloy heating material in the current market is lower, so that the heating film cannot achieve the effect of rapid temperature rise; in addition, the current manufacturing process of the alloy heating element has larger pollution waste discharge and has larger environmental hazard.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a safe heating film capable of absorbing the expansion of a battery without waste discharge.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a safety heating film capable of absorbing battery expansion without waste discharge, which comprises a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first protective layer and the second protective layer are made of the same material and are both modified polybenzimidazole materials.
Preferably, the thickness of the first cover protection layer is 300-800 μm, and the thickness of the second cover protection layer is 300-800 μm; the thickness of the first graphene conductive layer is 20-40 mu m, and the thickness of the second graphene conductive layer is 20-40 mu m.
Preferably, the first graphene conductive layer and the second graphene conductive layer are prepared by coating graphene conductive liquid, and the graphene conductive liquid comprises the following components in percentage by mass:
4% -10% of graphene, 0.5% -3.5% of polyethylene glycol 400, 0.2% -0.8% of fatty alcohol polyoxyethylene ether and the balance of N-methylpyrrolidone.
Preferably, the particle size of the graphene is 100-200nm.
Preferably, the preparation process of the safe heating film comprises the following steps:
a. uniformly mixing all components of the graphene conductive liquid to form the graphene conductive liquid;
b. respectively coating graphene conductive liquid on the lower surface of the first covering protective layer and the upper surface of the second covering protective layer, and drying to form a first graphene conductive layer and a second graphene conductive layer;
c. and fixing the electrode material on the upper surface of the second covering protection layer, enabling the lower surface of the first covering protection layer to face downwards, enabling the upper surface of the second covering protection layer to face upwards, and pressing the upper surface of the second covering protection layer together through a hot press to obtain the safe heating film.
Preferably, the preparation method of the modified polybenzimidazole material comprises the following steps:
step (1), preparing amino polybenzimidazole:
2, 3-diamino-5-nitrobenzoic acid is dissolved in solvent polyphosphoric acid, and is heated to react under the action of phosphorus pentoxide to obtain nitropolybenzimidazole; then carrying out catalytic hydrogenation reaction on the nitro polybenzimidazole to prepare amino polybenzimidazole;
step (2), preparing vinyl polybenzimidazole:
the preparation method comprises the steps of performing aldehyde-amine condensation reaction on amino polybenzimidazole and 4-vinyl benzaldehyde under the action of glacial acetic acid to prepare vinyl polybenzimidazole;
step (3), preparing a modified polybenzimidazole material:
the modified polybenzimidazole material is prepared by using vinyl polybenzimidazole and mercapto aluminum diboride to perform click reaction under the action of a photoinitiator and then performing tape casting film forming.
Preferably, the preparation process of the amino polybenzimidazole in the step (1) comprises the following steps:
s1, firstly weighing 2, 3-diamino-5-nitrobenzoic acid and dissolving in a solvent polyphosphoric acid ((P) 2 O 5 ) More than or equal to 85 percent), adding the weighed phosphorus pentoxide, fully stirring and dissolving, stirring and reacting for 12-18 hours at 180-200 ℃, cooling to room temperature after the reaction is finished, discharging to distilled water, dripping alkali liquor to pH=7, collecting precipitate, washing with water for at least three times, and drying to obtain nitropolybenzimidazole;
s2, mixing the nitropolybenzimidazole and absolute ethyl alcohol in a reaction kettle, adding a small amount of platinum-carbon catalyst, replacing air in the reaction kettle with nitrogen, then introducing hydrogen, controlling the pressure of the hydrogen to be 4-6MPa, heating to 45-55 ℃, reacting for 2-3h, removing the catalyst and the solvent, and drying to obtain the amino polybenzimidazole.
More preferably, in S1, the mass ratio of 2, 3-diamino-5-nitrobenzoic acid, phosphorus pentoxide and polyphosphoric acid is 0.39-0.78:0.08-0.16:10-20.
More preferably, in S2, the mass ratio of the nitropolybenzimidazole, the platinum carbon catalyst (60% Pt/C) and the absolute ethanol is 0.53-1.06:0.02-0.04:10-20.
Preferably, the preparation process of the vinyl polybenzimidazole in the step (2) comprises the following steps:
weighing amino polybenzimidazole, adding into dimethylbenzene, adding a small amount of glacial acetic acid, mixing uniformly, gradually adding 4-vinylbenzaldehyde under the ice bath condition, gradually heating after dripping, keeping the temperature to 75-95 ℃, reacting for 3-6 hours, naturally cooling to room temperature after the reaction is finished, removing the solvent, washing with water for three times, and drying to obtain the vinyl polybenzimidazole.
More preferably, the mass ratio of the amino polybenzimidazole, the 4-vinyl benzaldehyde, the glacial acetic acid and the xylene in the preparation process of the vinyl polybenzimidazole is 0.71-1.42:0.34-0.68:0.008-0.016:10-20.
Preferably, the preparation process of the aluminum mercapto diboride in the step (3) comprises the following steps:
placing nano aluminum diboride into absolute ethyl alcohol, heating and refluxing for 2-4 hours, and drying to obtain pretreated aluminum diboride; then mixing the pretreated aluminum diboride and a silane coupling agent KH-581 in distilled water, carrying out ultrasonic treatment at 30-40 ℃ for 8-16h, filtering out particles, washing with water for three times, and drying to obtain the sulfhydryl aluminum diboride;
more preferably, in the preparation process of the sulfhydryl aluminum diboride, the particle size of the nanometer aluminum diboride is 100-200nm; the mass ratio of the nanoscale aluminum diboride to the absolute ethyl alcohol is 1:5-15; the mass ratio of the pretreated aluminum diboride to the silane coupling agent KH-581 to the distilled water is 1:0.12-0.24:10-20.
Preferably, the preparation process of the modified polybenzimidazole material in the step (3) comprises the following steps:
sequentially adding vinyl polybenzimidazole and aluminum mercapto diboride into N, N-dimethylformamide, fully stirring, introducing inert gas as protective gas, adding a photoinitiator, stirring and reacting for 20-40min under the irradiation of ultraviolet light, vacuum defoamating after the reaction is finished, casting to form a film, and post-treating to obtain the modified polybenzimidazole material.
More preferably, in the preparation process of the modified polybenzimidazole material, the photoinitiator comprises 2, 2-dimethoxy-2-phenylacetophenone or benzophenone, the addition amount of the photoinitiator is 2% -5% of the mass of vinyl polybenzimidazole, and the ultraviolet wavelength is 365nm.
More preferably, in the preparation process of the modified polybenzimidazole material, the mass ratio of the vinyl polybenzimidazole to the aluminum mercapto diboride to the N, N-dimethylformamide is 1:0.23-0.46:10-20.
More preferably, the casting film forming and post-treatment process includes: casting the defoamed reaction solution on a clean glass plate to form a film, firstly drying at 100-120 ℃ for 6-12h, then treating at 150-160 ℃ for 1h, then soaking in distilled water for 4-10h, and finally drying in vacuum.
The beneficial effects of the invention are as follows:
1. the protective layer of the safe heating film is prepared from a special modified polybenzimidazole material, has higher strength and toughness, and can absorb the expansion of a battery to ensure the use safety of the battery; in addition, the safe heating film uses the graphene conductive layer to replace alloy materials in the market, so that the defect that the manufacturing of an alloy heating body is harmful to the environment is overcome, and the heating is more uniform.
2. The components of the first protective layer and the second protective layer are modified polybenzimidazole materials, and the preparation process comprises the following steps: (1) Firstly, preparing nitro polybenzimidazole, and carrying out catalytic hydrogenation reaction to obtain amino polybenzimidazole; (2) Reacting amino polybenzimidazole with 4-vinyl benzaldehyde, and performing condensation reaction on amino and aldehyde groups to generate Schiff base; (3) Then reacts with aluminum mercapto diboride, and the mercapto reacts with double bond to generate thioether bond, thus preparing the modified polybenzimidazole material. And (3) after the modified polybenzimidazole material is subjected to tape casting film forming and post-treatment, respectively forming a first protective cover and a second protective cover.
3. The graphene conductive liquid prepared by the method forms a graphene conductive layer after being coated and dried, and compared with alloy materials in the market, the graphene conductive liquid has the advantages of less pollution waste discharge and more uniform heating conduction.
4. The polybenzimidazole material has the greatest characteristics of strong instantaneous high temperature resistance, but general strength and toughness. The modified polybenzimidazole material prepared by the invention is used as a protective layer, and has better mechanical property and flexibility than the traditional polybenzimidazole material, thereby playing a better protective role; and the battery also has higher heat conductivity, and can release heat to the battery more rapidly, so that the temperature control of the battery is more sensitive.
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
A waste discharge-free safe heating film capable of absorbing battery expansion comprises a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first protective layer and the second protective layer are made of the same material and are both modified polybenzimidazole materials. The thickness of the first cover protection layer is 500 μm, and the thickness of the second cover protection layer is 500 μm; the thickness of the first graphene conductive layer is 30 μm and the thickness of the second graphene conductive layer is 30 μm.
The first graphene conductive layer and the second graphene conductive layer are prepared by coating graphene conductive liquid, and the graphene conductive liquid comprises the following components in percentage by mass:
6% of graphene with the particle size of 100-200nm, 2.5% of polyethylene glycol 400, 0.5% of fatty alcohol polyoxyethylene ether and the balance of N-methylpyrrolidone.
The preparation process of the safe heating film comprises the following steps:
a. uniformly mixing all components of the graphene conductive liquid to form the graphene conductive liquid;
b. respectively coating graphene conductive liquid on the lower surface of the first covering protective layer and the upper surface of the second covering protective layer, and drying to form a first graphene conductive layer and a second graphene conductive layer;
c. and fixing the electrode material on the upper surface of the second covering protection layer, enabling the lower surface of the first covering protection layer to face downwards, enabling the upper surface of the second covering protection layer to face upwards, and pressing the upper surface of the second covering protection layer together through a hot press to obtain the safe heating film.
The preparation method of the modified polybenzimidazole material comprises the following steps:
step (1), preparing amino polybenzimidazole:
s1, firstly weighing 2, 3-diamino-5-nitrobenzoic acid, dissolving in a solvent polyphosphoric acid ((P2O 5)% > 85%), then adding the weighed phosphorus pentoxide, fully stirring for dissolving, stirring at 200 ℃ for reaction for 15 hours, cooling to room temperature after the reaction is finished, discharging to distilled water, dropwise adding alkali liquor to pH=7, collecting precipitate, washing with water for at least three times, and drying to obtain nitropolybenzimidazole; wherein the mass ratio of the 2, 3-diamino-5-nitrobenzoic acid, the phosphorus pentoxide and the polyphosphoric acid is 0.59:0.12:15.
S2, mixing nitropolybenzimidazole and absolute ethyl alcohol in a reaction kettle, adding a small amount of platinum-carbon catalyst, replacing air in the reaction kettle with nitrogen, then introducing hydrogen, controlling the pressure of the hydrogen to be 5MPa, heating to 50 ℃, reacting for 2.5 hours, removing the catalyst and the solvent, and drying to obtain amino polybenzimidazole; wherein the mass ratio of the nitropolybenzimidazole, the platinum carbon catalyst (60% Pt/C) and the absolute ethanol is 0.79:0.03:15.
Step (2), preparing vinyl polybenzimidazole:
weighing amino polybenzimidazole, adding into dimethylbenzene, adding a small amount of glacial acetic acid, mixing uniformly, gradually adding 4-vinylbenzaldehyde under the ice bath condition, gradually heating after dripping, keeping the temperature to 85 ℃, reacting for 5 hours, naturally cooling to room temperature after the reaction is finished, removing the solvent, washing for three times, and drying to obtain vinyl polybenzimidazole; wherein, in the preparation process of the vinyl polybenzimidazole, the mass ratio of the amino polybenzimidazole, the 4-vinyl benzaldehyde, the glacial acetic acid and the dimethylbenzene is 1.07:0.51:0.016:15.
Step (3), preparing a modified polybenzimidazole material:
placing aluminum diboride with the particle size of 100-200nm into absolute ethyl alcohol, heating and refluxing for 3 hours, and drying to obtain pretreated aluminum diboride; wherein the mass ratio of the nanoscale aluminum diboride to the absolute ethyl alcohol is 1:10; then mixing the pretreated aluminum diboride with a silane coupling agent KH-581 in distilled water, carrying out ultrasonic treatment at 35 ℃ for 12 hours, filtering out particles, washing with water for three times, and drying to obtain the sulfhydryl aluminum diboride; wherein the mass ratio of the pretreated aluminum diboride to the silane coupling agent KH-581 to the distilled water is 1:0.18:15.
Sequentially adding vinyl polybenzimidazole and aluminum mercapto diboride into N, N-dimethylformamide, fully stirring, introducing inert gas as protective gas, adding a photoinitiator, stirring and reacting for 30min under the irradiation of ultraviolet light, vacuum defoaming after the reaction is finished, casting the defoamed reaction solution on a clean glass plate to form a film, firstly drying at 100 ℃ for 8h, then treating at 160 ℃ for 1h, then soaking in distilled water for 6h, and finally vacuum drying to obtain the modified polybenzimidazole material.
Wherein the photoinitiator is 2, 2-dimethoxy-2-phenyl acetophenone, the addition amount of the photoinitiator is 3% of the mass of vinyl polybenzimidazole, and the ultraviolet wavelength is 365nm. The mass ratio of the vinyl polybenzimidazole, the aluminum mercapto diboride and the N, N-dimethylformamide is 1:0.35:15.
Example 2
A waste discharge-free safe heating film capable of absorbing battery expansion comprises a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first protective layer and the second protective layer are made of the same material and are both modified polybenzimidazole materials. The thickness of the first cover protection layer is 300 μm, and the thickness of the second cover protection layer is 300 μm; the thickness of the first graphene conductive layer is 20 μm and the thickness of the second graphene conductive layer is 20 μm.
The first graphene conductive layer and the second graphene conductive layer are prepared by coating graphene conductive liquid, and the graphene conductive liquid comprises the following components in percentage by mass:
4% of graphene with the particle size of 100-200nm, 0.5% of polyethylene glycol 400, 0.2% of fatty alcohol polyoxyethylene ether and the balance of N-methylpyrrolidone.
The preparation process of the safe heating film comprises the following steps:
a. uniformly mixing all components of the graphene conductive liquid to form the graphene conductive liquid;
b. respectively coating graphene conductive liquid on the lower surface of the first covering protective layer and the upper surface of the second covering protective layer, and drying to form a first graphene conductive layer and a second graphene conductive layer;
c. and fixing the electrode material on the upper surface of the second covering protection layer, enabling the lower surface of the first covering protection layer to face downwards, enabling the upper surface of the second covering protection layer to face upwards, and pressing the upper surface of the second covering protection layer together through a hot press to obtain the safe heating film.
The preparation method of the modified polybenzimidazole material comprises the following steps:
step (1), preparing amino polybenzimidazole:
s1, firstly weighing 2, 3-diamino-5-nitrobenzoic acid, dissolving in a solvent polyphosphoric acid ((P2O 5)% > 85%), then adding the weighed phosphorus pentoxide, fully stirring for dissolving, stirring at 180 ℃ for reacting for 12 hours, cooling to room temperature after the reaction is finished, discharging to distilled water, dropwise adding alkali liquor to pH=7, collecting precipitate, washing with water for at least three times, and drying to obtain nitropolybenzimidazole; wherein the mass ratio of the 2, 3-diamino-5-nitrobenzoic acid, the phosphorus pentoxide and the polyphosphoric acid is 0.39:0.08:10.
S2, mixing nitropolybenzimidazole and absolute ethyl alcohol in a reaction kettle, adding a small amount of platinum-carbon catalyst, replacing air in the reaction kettle with nitrogen, then introducing hydrogen, controlling the pressure of the hydrogen to be 4MPa, heating to 45 ℃, reacting for 2 hours, removing the catalyst and the solvent, and drying to obtain amino polybenzimidazole; wherein the mass ratio of the nitropolybenzimidazole, the platinum carbon catalyst (60% Pt/C) and the absolute ethanol is 0.53:0.02:10.
Step (2), preparing vinyl polybenzimidazole:
weighing amino polybenzimidazole, adding into dimethylbenzene, adding a small amount of glacial acetic acid, mixing uniformly, gradually adding 4-vinylbenzaldehyde under the ice bath condition, gradually heating after dripping, keeping the temperature at 75 ℃, reacting for 3 hours, naturally cooling to room temperature after the reaction is finished, removing the solvent, washing for three times, and drying to obtain vinyl polybenzimidazole; wherein, in the preparation process of the vinyl polybenzimidazole, the mass ratio of the amino polybenzimidazole, the 4-vinyl benzaldehyde, the glacial acetic acid and the dimethylbenzene is 0.71:0.34:0.008:10.
Step (3), preparing a modified polybenzimidazole material:
placing aluminum diboride with the particle size of 100-200nm into absolute ethyl alcohol, heating and refluxing for 2 hours, and drying to obtain pretreated aluminum diboride; then mixing the pretreated aluminum diboride with a silane coupling agent KH-581 in distilled water, carrying out ultrasonic treatment at 30 ℃ for 8 hours, filtering out particles, washing with water for three times, and drying to obtain the sulfhydryl aluminum diboride; wherein the mass ratio of the nanoscale aluminum diboride to the absolute ethyl alcohol is 1:5; the mass ratio of the pretreated aluminum diboride, the silane coupling agent KH-581 and distilled water is 1:0.12:10.
Sequentially adding vinyl polybenzimidazole and aluminum mercapto diboride into N, N-dimethylformamide, fully stirring, introducing inert gas as protective gas, adding a photoinitiator, stirring and reacting for 20min under the irradiation of ultraviolet light, vacuum defoaming after the reaction is finished, casting the defoamed reaction solution on a clean glass plate to form a film, firstly drying at 100 ℃ for 6h, then treating at 150 ℃ for 1h, then soaking in distilled water for 4h, and finally vacuum drying to obtain the modified polybenzimidazole material.
Wherein the photoinitiator is diphenyl ketone, the addition amount of the photoinitiator is 2% of the mass of vinyl polybenzimidazole, and the ultraviolet wavelength is 365nm. The mass ratio of the vinyl polybenzimidazole, the aluminum mercapto diboride and the N, N-dimethylformamide is 1:0.23:10.
Example 3
A waste discharge-free safe heating film capable of absorbing battery expansion comprises a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first protective layer and the second protective layer are made of the same material and are both modified polybenzimidazole materials. The thickness of the first cover protection layer is 800 μm, and the thickness of the second cover protection layer is 800 μm; the thickness of the first graphene conductive layer is 40 μm and the thickness of the second graphene conductive layer is 40 μm.
The first graphene conductive layer and the second graphene conductive layer are prepared by coating graphene conductive liquid, and the graphene conductive liquid comprises the following components in percentage by mass:
10% of graphene with the particle size of 100-200nm, 3.5% of polyethylene glycol 400, 0.8% of fatty alcohol polyoxyethylene ether and the balance of N-methylpyrrolidone.
The preparation process of the safe heating film comprises the following steps:
a. uniformly mixing all components of the graphene conductive liquid to form the graphene conductive liquid;
b. respectively coating graphene conductive liquid on the lower surface of the first covering protective layer and the upper surface of the second covering protective layer, and drying to form a first graphene conductive layer and a second graphene conductive layer;
c. and fixing the electrode material on the upper surface of the second covering protection layer, enabling the lower surface of the first covering protection layer to face downwards, enabling the upper surface of the second covering protection layer to face upwards, and pressing the upper surface of the second covering protection layer together through a hot press to obtain the safe heating film.
The preparation method of the modified polybenzimidazole material comprises the following steps:
step (1), preparing amino polybenzimidazole:
s1, firstly weighing 2, 3-diamino-5-nitrobenzoic acid, dissolving in a solvent polyphosphoric acid ((P2O 5)% > 85%), then adding the weighed phosphorus pentoxide, fully stirring for dissolving, stirring for reacting for 12-18 hours at 200 ℃, cooling to room temperature after the reaction is finished, discharging to distilled water, dropwise adding alkali liquor to pH=7, collecting precipitate, washing with water for at least three times, and drying to obtain nitropolybenzimidazole; wherein the mass ratio of the 2, 3-diamino-5-nitrobenzoic acid, the phosphorus pentoxide and the polyphosphoric acid is 0.78:0.16:20.
S2, mixing nitropolybenzimidazole and absolute ethyl alcohol in a reaction kettle, adding a small amount of platinum-carbon catalyst, replacing air in the reaction kettle with nitrogen, then introducing hydrogen, controlling the pressure of the hydrogen to be 6MPa, heating to 55 ℃, reacting for 3 hours, removing the catalyst and the solvent, and drying to obtain amino polybenzimidazole; wherein the mass ratio of the nitropolybenzimidazole to the platinum carbon catalyst (60% Pt/C) to the absolute ethanol is 1.06:0.04:20.
Step (2), preparing vinyl polybenzimidazole:
weighing amino polybenzimidazole, adding into dimethylbenzene, adding a small amount of glacial acetic acid, mixing uniformly, gradually adding 4-vinylbenzaldehyde under the ice bath condition, gradually heating after dripping, keeping the temperature to 95 ℃, reacting for 6 hours, naturally cooling to room temperature after the reaction is finished, removing the solvent, washing for three times, and drying to obtain vinyl polybenzimidazole; wherein, in the preparation process of the vinyl polybenzimidazole, the mass ratio of the amino polybenzimidazole, the 4-vinyl benzaldehyde, the glacial acetic acid and the dimethylbenzene is 1.42:0.68:0.016:20.
Step (3), preparing a modified polybenzimidazole material:
placing aluminum diboride with the particle size of 100-200nm into absolute ethyl alcohol, heating and refluxing for 4 hours, and drying to obtain pretreated aluminum diboride; then mixing the pretreated aluminum diboride with a silane coupling agent KH-581 in distilled water, carrying out ultrasonic treatment at 40 ℃ for 16 hours, filtering out particles, washing with water for three times, and drying to obtain the sulfhydryl aluminum diboride; wherein the mass ratio of the nanoscale aluminum diboride to the absolute ethyl alcohol is 1:15; the mass ratio of the pretreated aluminum diboride, the silane coupling agent KH-581 and distilled water is 1:0.24:20.
Sequentially adding vinyl polybenzimidazole and aluminum mercapto diboride into N, N-dimethylformamide, fully stirring, introducing inert gas as protective gas, adding a photoinitiator, stirring and reacting for 40min under the irradiation of ultraviolet light, vacuum defoaming after the reaction is finished, casting the defoamed reaction solution on a clean glass plate to form a film, firstly drying at 120 ℃ for 12h, then treating at 160 ℃ for 1h, then soaking in distilled water for 10h, and finally vacuum drying to obtain the modified polybenzimidazole material.
Wherein the photoinitiator is diphenyl ketone, the addition amount of the photoinitiator is 5% of the mass of vinyl polybenzimidazole, and the ultraviolet wavelength is 365nm. The mass ratio of the vinyl polybenzimidazole, the aluminum mercapto diboride and the N, N-dimethylformamide is 1:0.46:20.
Comparative example 1
The difference between the heating film and example 1 is that the materials of the first protective cover layer and the second protective cover layer are different from example 1, the material used in this comparative example is polybenzimidazole material, which is a polybenzimidazole resin with the model number of U-60SD and is commercially available, and the film forming process is to dissolve amino polybenzimidazole in N, N-dimethylformamide, and then to form a film by casting film according to example 1.
Comparative example 2
A heating film was different from example 1 in that the first and second protective layers were each made of an amino polybenzimidazole, which was prepared in the same manner as in step (1) of example 1, and was formed by dissolving amino polybenzimidazole in N, N-dimethylformamide and then casting the film according to example 1.
Comparative example 3
The heating film was different from example 1 in that the first and second protective layers were each made of a modified polybenzimidazole material, but the preparation method was different from example 1.
The preparation method of the modified polybenzimidazole material of the comparative example comprises the following steps: the amino polybenzimidazole, aluminum diboride and N, N-dimethylformamide are mixed according to the mass ratio of 1:0.35:15, and after being fully stirred, the mixture is formed into a film by the casting film forming mode of the example 1.
Wherein the amino polybenzimidazole was prepared in the same manner as in the step (1) of example 1, and the aluminum diboride particle size was 100 to 200nm.
Experimental example
The materials for covering the protective layers prepared in example 1, comparative example 2, and comparative example 3 were tested, and the tensile strength and elongation at break test standard was referred to GB/T1040-2006, and the impact strength test standard was referred to GB/T1843-2008.
The test results are shown in Table 1:
table 1 results of performance tests for different methods of preparing the cover protection layer
As can be seen from table 1, the covering protection layer prepared in the embodiment 1 of the invention has strong high temperature resistance, and greatly improved tensile strength and impact strength, which indicates that the strength and toughness are more excellent, so that the safety of the battery can be further ensured; the heat conductivity coefficient is also greatly improved, which means that the heat transfer can be faster and the heat conduction efficiency is enhanced. The protective cover layer prepared in example 1 of the present invention is very suitable for use as a battery heating film as a whole.
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 (9)

1. The safety heating film is characterized by comprising a first covering protection layer, a first graphene conductive layer, an electrode material, a second graphene conductive layer and a second covering protection layer which are sequentially arranged from top to bottom; the first cover protection layer and the second cover protection layer are the same in material and are both modified polybenzimidazole materials;
the preparation method of the modified polybenzimidazole material comprises the following steps:
step (1), preparing amino polybenzimidazole:
2, 3-diamino-5-nitrobenzoic acid is dissolved in solvent polyphosphoric acid, and is heated to react under the action of phosphorus pentoxide to obtain nitropolybenzimidazole; then carrying out catalytic hydrogenation reaction on the nitro polybenzimidazole to prepare amino polybenzimidazole;
step (2), preparing vinyl polybenzimidazole:
the preparation method comprises the steps of performing aldehyde-amine condensation reaction on amino polybenzimidazole and 4-vinyl benzaldehyde under the action of glacial acetic acid to prepare vinyl polybenzimidazole;
step (3), preparing a modified polybenzimidazole material:
the modified polybenzimidazole material is prepared by using vinyl polybenzimidazole and mercapto aluminum diboride to perform click reaction under the action of a photoinitiator and then performing tape casting film forming.
2. The waste discharge free absorbable battery expanded safe heating film of claim 1, wherein the first protective cover layer has a thickness of 300-800 μm and the second protective cover layer has a thickness of 300-800 μm; the thickness of the first graphene conductive layer is 20-40 mu m, and the thickness of the second graphene conductive layer is 20-40 mu m.
3. The waste discharge-free safe heating film capable of absorbing battery expansion according to claim 1, wherein the first graphene conductive layer and the second graphene conductive layer are prepared by coating graphene conductive liquid, and the graphene conductive liquid comprises the following components in percentage by mass:
4% -10% of graphene, 0.5% -3.5% of polyethylene glycol 400, 0.2% -0.8% of fatty alcohol polyoxyethylene ether and the balance of N-methylpyrrolidone.
4. The safety heating film for expansion of waste discharge-free absorbable battery of claim 1, wherein said step (1) comprises the steps of:
s1, firstly weighing 2, 3-diamino-5-nitrobenzoic acid, dissolving in a solvent polyphosphoric acid ((P2O 5)% > 85%), then adding the weighed phosphorus pentoxide, fully stirring for dissolving, stirring and reacting for 12-18 hours at 180-200 ℃, cooling to room temperature after the reaction is finished, discharging to distilled water, dropwise adding alkali liquor to pH=7, collecting precipitate, washing with water for at least three times, and drying to obtain nitropolybenzimidazole;
s2, mixing the nitropolybenzimidazole and absolute ethyl alcohol in a reaction kettle, adding a small amount of platinum-carbon catalyst, replacing air in the reaction kettle with nitrogen, then introducing hydrogen, controlling the pressure of the hydrogen to be 4-6MPa, heating to 45-55 ℃, reacting for 2-3h, removing the catalyst and the solvent, and drying to obtain the amino polybenzimidazole.
5. The safety heating film for expanding a waste discharge-free absorbable battery according to claim 1, wherein the preparation process of the vinyl polybenzimidazole in the step (2) comprises the following steps:
weighing amino polybenzimidazole, adding into dimethylbenzene, adding a small amount of glacial acetic acid, mixing uniformly, gradually adding 4-vinylbenzaldehyde under the ice bath condition, gradually heating after dripping, keeping the temperature to 75-95 ℃, reacting for 3-6 hours, naturally cooling to room temperature after the reaction is finished, removing the solvent, washing for three times, and drying to obtain vinyl polybenzimidazole;
wherein the mass ratio of the amino polybenzimidazole to the 4-vinyl benzaldehyde to the glacial acetic acid to the dimethylbenzene is 0.71-1.42:0.34-0.68:0.008-0.016:10-20.
6. The waste discharge free, absorbent battery swelling safety heating film of claim 5, wherein the process of preparing aluminum mercapto diboride in step (3) comprises:
placing nano aluminum diboride into absolute ethyl alcohol, heating and refluxing for 2-4 hours, and drying to obtain pretreated aluminum diboride; then mixing the pretreated aluminum diboride and a silane coupling agent KH-581 in distilled water, carrying out ultrasonic treatment at 30-40 ℃ for 8-16h, filtering out particles, washing with water for three times, and drying to obtain the sulfhydryl aluminum diboride;
wherein, in the preparation process of the sulfhydryl aluminum diboride, the grain diameter of the nanometer aluminum diboride is 100-200nm; the mass ratio of the nanoscale aluminum diboride to the absolute ethyl alcohol is 1:5-15; the mass ratio of the pretreated aluminum diboride to the silane coupling agent KH-581 to the distilled water is 1:0.12-0.24:10-20.
7. The safety heating film for expanding a waste discharge-free absorbable battery according to claim 4, wherein the preparation process of the modified polybenzimidazole material in the step (3) comprises the following steps:
sequentially adding vinyl polybenzimidazole and aluminum mercapto diboride into N, N-dimethylformamide, fully stirring, introducing inert gas as a protective gas, adding a photoinitiator, stirring and reacting for 20-40min under the irradiation of ultraviolet light, vacuum defoamating after the reaction is finished, casting to form a film, and post-treating to obtain a modified polybenzimidazole material;
wherein, in the preparation process of the modified polybenzimidazole material, the mass ratio of the vinyl polybenzimidazole to the aluminum mercapto diboride to the N, N-dimethylformamide is 1:0.23-0.46:10-20.
8. The safety heating film for expanding waste discharge-free absorbable battery as claimed in claim 7, wherein the photoinitiator comprises 2, 2-dimethoxy-2-phenyl acetophenone or diphenyl ketone, the addition amount of the photoinitiator is 2% -5% of the mass of vinyl polybenzimidazole, and the ultraviolet wavelength is 365nm.
9. The waste-free absorbable battery expansion safe heating film of claim 7, wherein the cast film and post-treatment process comprises: casting the defoamed reaction solution on a clean glass plate to form a film, firstly drying at 100-120 ℃ for 6-12h, then treating at 150-160 ℃ for 1h, then soaking in distilled water for 4-10h, and finally drying in vacuum.
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