CN110815993A - Battery protective layer, preparation method and application of battery protective layer in battery assembly - Google Patents
Battery protective layer, preparation method and application of battery protective layer in battery assembly Download PDFInfo
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- CN110815993A CN110815993A CN201810903431.7A CN201810903431A CN110815993A CN 110815993 A CN110815993 A CN 110815993A CN 201810903431 A CN201810903431 A CN 201810903431A CN 110815993 A CN110815993 A CN 110815993A
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- 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
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- 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
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- 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
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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
- 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
- H01M50/24—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 from their environment, e.g. from corrosion
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Mounting, Suspending (AREA)
Abstract
The invention provides a battery protective layer, a preparation method and application of the battery protective layer in a battery assembly. The battery protective layer has the characteristics of high strength, ablation resistance, thermal shock resistance and flame retardance, can bear explosion impact, block sparks and inhibit combustion diffusion, effectively avoids the ignition or explosion of the battery, and improves the safety of the battery in the using process.
Description
Technical Field
The invention relates to the field of batteries, in particular to a battery protective layer, a preparation method and application thereof in a battery assembly.
Background
The power battery is used as a core component of the new energy automobile and has a key influence on the performance of the new energy automobile. With the development of new energy automobile industry, the market has more urgent needs for the performance of high-power output, quick charge and discharge and the like of the power battery, but the more severe requirements are provided for the safety performance of the power battery in the using process. Especially, in recent years, the safety problem of the power battery is more and more prominent due to frequent safety accidents of the power battery, and the safety problem of the power battery greatly limits the rapid development of new energy automobiles.
The safety problem of the power battery is closely related to thermal runaway in nature, when the thermal runaway occurs to the power battery due to various reasons in the using process, such as increased heat generation inside the battery during high-power output or rapid charge and discharge, accidental impact and the like, active substance particles inside the single battery can be ejected from an explosion-proof port in a spark form to directly impact the battery module or the upper cover of the battery pack, so that the upper cover is decomposed or melted in a short time, and the fire spreads to other single batteries inside the battery pack or other battery modules or even the inside of a vehicle, thereby endangering the safety of the whole vehicle and the personal safety of personnel in the vehicle.
Disclosure of Invention
In view of the problems in the background art, the present invention is directed to a battery protection layer, a method for manufacturing the same, and an application of the battery protection layer in a battery module, wherein the battery protection layer has characteristics of high strength, ablation resistance, thermal shock resistance, and flame retardancy, and can bear explosion impact, block sparks, and inhibit combustion diffusion, thereby effectively preventing a battery from being ignited or exploded, and improving safety of the battery during use.
In order to achieve the purpose, the invention provides a battery protective layer which comprises fireproof cloth and a functional layer arranged on the fireproof cloth, wherein the functional layer is a thermosetting resin layer mainly formed by curing an epoxy resin matrix, an epoxy resin curing agent, a reinforcing filler, a flame retardant and a silane coupling agent.
In order to achieve the above object, the present invention also provides a method for preparing a battery protective layer, comprising the steps of: dissolving an epoxy resin matrix in a solvent to obtain an epoxy resin matrix solution; then adding the reinforcing filler and the flame retardant into the epoxy resin matrix solution, uniformly mixing, then adding the silane coupling agent, uniformly mixing again, adding the epoxy resin curing agent, and uniformly stirring to obtain a mixed solution; and fully soaking the mixed solution into the fireproof cloth, then covering the fireproof cloth on the body material, standing at room temperature or heating to cure the epoxy resin matrix in the mixed solution to form a thermal curing resin layer, and finishing the preparation of the battery protective layer.
In order to achieve the above object, the present invention further provides an application of the battery protection layer in a battery module, wherein the battery module is a battery module or a battery pack.
Compared with the prior art, the invention at least comprises the following beneficial effects:
the battery protective layer has the characteristics of high strength, ablation resistance, thermal shock resistance and flame retardance, can bear explosion impact, block sparks and inhibit combustion diffusion, effectively avoids the ignition or explosion of the battery, and improves the safety of the battery in the using process.
Detailed Description
The protective layer for a battery, the preparation method thereof, and the use thereof in a battery pack according to the present invention will be described in detail below.
First, the battery protective layer according to the present invention will be described.
The battery protective layer comprises fireproof cloth and a functional layer arranged on the fireproof cloth, wherein the functional layer is a thermosetting resin layer mainly formed by curing an epoxy resin matrix, an epoxy resin curing agent, a reinforcing filler, a flame retardant and a silane coupling agent.
In the battery protective layer, the epoxy resin matrix and the epoxy resin curing agent are matched to react, so that an epoxy group in the epoxy resin matrix can generate ring-opening polymerization reaction, the functional layer is bonded to the fireproof cloth, and meanwhile, a high-temperature-resistant and thermal-shock-resistant thermosetting resin layer is generated, so that the battery protective layer can effectively bear explosion impact and block sparks. The existence of the reinforcing filler and the fireproof cloth can provide double support for the structure of the battery protective layer, so that the battery protective layer has higher strength, better bears the explosion impact and better blocks sparks. The flame retardant can generate free radicals at high temperature to combine with hydrogen atoms in a flame area, so that the effects of extinguishing sparks and inhibiting continuous combustion are achieved, and the flame retardant effect of a battery protective layer is enhanced. The silane coupling agent is an organic silicon compound containing two groups with different chemical properties in a molecule, and the molecule of the silane coupling agent simultaneously has a reaction group capable of being chemically combined with the reinforcing filler and a reaction group capable of being chemically combined with the epoxy resin matrix, so that the compatibility, the wettability and the dispersibility of the reinforcing filler and the epoxy resin matrix can be improved, and the durability of the functional layer is further improved.
In the battery protective layer, when the temperature of the thermosetting resin layer is continuously increased, for example, the temperature is higher than 500 ℃, the thermosetting resin layer is pyrolyzed and generates a compact carbon layer protective layer, so that the battery protective layer is prevented from being directly burnt by flame, and meanwhile, the compact carbon layer protective layer can also have good flame retardant property, and the battery is effectively prevented from being ignited or exploded. In addition, harmful gas can not be generated when the thermosetting resin layer is pyrolyzed, personal safety can not be endangered, and the environment can not be polluted.
Therefore, the battery protective layer has the characteristics of high strength, ablation resistance, thermal shock resistance and flame retardance, can bear explosion impact, obstruct sparks, inhibit combustion diffusion and even self-extinguish, effectively avoids the ignition or explosion of the battery, and improves the safety of the battery in the using process.
The battery protective layer provided by the invention is low in cost and can be applied on a large scale.
In the battery protective layer of the present invention, the type of the flameproof fabric is not particularly limited, and preferably, the flameproof fabric is selected from one or more of glass fiber fabric, basalt fiber fabric, acrylic cotton fiber fabric, and carbon fiber fabric.
In the battery protective layer of the present invention, the kind of the epoxy resin matrix is not particularly limited, and preferably, the epoxy resin matrix is selected from one or more of silicone-modified epoxy resin, phenol-modified epoxy resin, maleimide-modified epoxy resin, and benzoxazine-modified epoxy resin. The epoxy resin matrixes help to generate a denser carbon layer protective layer when the battery protective layer is pyrolyzed, and the combustion diffusion is better prevented from being inhibited. Wherein the epoxy resin can be glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or alicyclic epoxy resin.
In the battery protective layer according to the present invention, preferably, the curing temperature of the epoxy resin curing agent is 25 to 100 ℃. The kind of the epoxy resin curing agent is not particularly limited as long as it can ring-open polymerize the epoxy resin matrix. Preferably, the epoxy resin curing agent is selected from one or more of imidazoles, acid anhydrides, polyamides, tertiary amines, boron trifluoride and complexes thereof.
In the battery protective layer according to the present invention, the kind of the reinforcing filler is not particularly limited, and preferably, the reinforcing filler is selected from one or more of glass fiber, carbon fiber, basalt fiber, quartz fiber, and asbestos fiber.
In the battery protective layer of the present invention, the kind of the flame retardant is not particularly limited, and preferably, the flame retardant is a phosphorus-containing flame retardant. Further preferably, the flame retardant is selected from one or more of phosphate, ammonium polyphosphate, phosphate and phosphite.
In the battery protective layer of the present invention, the kind of the silane coupling agent is not particularly limited, and may be appropriately optimized according to the kind of the epoxy resin matrix. Preferably, the silane coupling agent is selected from one or more of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane.
In the battery protective layer of the present invention, preferably, the functional layer includes:
40-80 parts by mass of an epoxy resin matrix;
20-40 parts by mass of an epoxy resin curing agent;
20-60 parts by mass of a reinforcing filler;
5-40 parts by mass of a flame retardant;
0.5-2 parts by mass of a silane coupling agent.
In the battery protective layer according to the present invention, preferably, the thickness of the battery protective layer is 0.5mm to 3 mm. The thickness is too small, and the fireproof and flame-retardant effects are poor; too large thickness will increase the weight of the battery protective layer and increase the manufacturing cost of the battery.
Next, a method for preparing a protective layer of a battery according to the present invention will be described.
The preparation method of the battery protective layer comprises the following steps: (1) dissolving an epoxy resin matrix in a solvent to obtain an epoxy resin matrix solution; (2) then adding the reinforcing filler and the flame retardant into the epoxy resin matrix solution, uniformly mixing, then adding the silane coupling agent, uniformly mixing again, adding the epoxy resin curing agent, and uniformly stirring to obtain a mixed solution; (3) and fully soaking the mixed solution into the fireproof cloth, then covering the fireproof cloth on the body material, standing at room temperature or heating to cure the epoxy resin matrix in the mixed solution to form a thermal curing resin layer, and finishing the preparation of the battery protective layer.
In the method for producing the battery protective layer, the kind of the solvent is not particularly limited, and preferably, the solvent may be one or more selected from acetone, methyl ethyl ketone, diethylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether, and ethyl acetate.
In the preparation method of the battery protective layer, the arrangement mode of the mixed solution on the surface of the fireproof cloth is not particularly limited, and the mixed solution can be brush coating, spray coating or dip coating, and can also be other conventional coating modes.
In the preparation method of the battery protective layer, the curing temperature of the epoxy resin matrix can be 25-100 ℃, and the curing time can be 2-6 h.
In the preparation method of the battery protection layer, the material of the body material is not particularly limited, and may be a metal material, such as aluminum, steel or alloy, or a non-metal material, such as plastic, composite material (e.g., long fiber reinforced thermoplastic material LFT), and the like.
In the preparation method of the battery protective layer, the body material can also be a battery module upper cover, a battery module wire harness isolation plate or a battery pack upper cover, the mixed liquid is directly covered on the inner side position of the battery module upper cover, the battery module wire harness isolation plate or the battery pack upper cover after being fully soaked in the fireproof cloth and is subjected to curing treatment, so that the thermosetting resin layer can be combined with the battery module or the battery pack more firmly and is not easy to fall off or deform, meanwhile, a compact carbon layer protective layer generated by pyrolysis of the thermosetting resin layer can also play a good flame retardant property, and the battery module or the battery pack is effectively prevented from being ignited or exploded. In addition, the mixed liquid is fully soaked in the fireproof cloth and then directly covers the inner side positions of the upper cover of the battery module, the wiring harness isolation plate of the battery module or the upper cover of the battery pack and is subjected to curing treatment, the use of parts in the assembling process of the battery module and the battery pack can be reduced, the process is simplified, and the manufacturing cost is reduced.
The application of the battery protection layer according to the present invention in a battery module, wherein the battery module is a battery module or a battery pack, is described again.
Generally, a battery pack includes a lower case and an upper cover, the lower case and the upper cover form an accommodating space for accommodating battery modules, and more than two battery modules may be disposed in the accommodating space. In the battery pack, the battery modules may be arranged in one or more than two rows, each battery module may include a plurality of unit batteries, and an end plate, a side plate, a bottom plate, and an upper cover that cover the plurality of unit batteries, and each battery module further includes a wire harness partition plate. Each unit cell may include a battery case, a cap assembly connected to the battery case, and an electrode assembly received between the battery case and the cap assembly.
The battery protective layer according to the present invention may be used in a battery module, the specific application location of which within the battery module is not particularly limited. For example, the battery protective layer can be compounded with the body material and then placed above the single battery top cover assembly, preferably between the single battery top cover assembly and the upper cover of the battery module; the battery protective layer may also be directly combined with structural components in the battery module, such as a battery module upper cover, a battery module harness isolation plate, and the like, and specifically, the battery protective layer may be disposed on an inner side of the battery module upper cover or an inner side of the battery module harness isolation plate. The battery protection layer may be disposed at one position or at a plurality of positions in the battery module. Like this, thermal runaway appears in a certain battery cell, the inside active material granule of battery cell sprays out the back from the explosion vent of top cap subassembly with the form of spark, the battery inoxidizing coating that sets up in the battery module can bear the explosion well and assault and separation spark, prevent effectively that the battery module upper cover from being directly strikeed by spark, delay or prevent that the battery module upper cover is decomposed or melt in the short time, the battery inoxidizing coating that sets up in the battery module simultaneously can also restrain the diffusion of burning, even make it from putting out, finally effectively avoid the battery module to catch fire or explode, the security in the improvement battery module use. In addition, the battery protective layer of the top cover assembly of the single battery can also play a role in preventing fire from spreading to other single batteries.
The battery protective layer according to the present invention may also be used in a battery pack, and its specific application position within the battery pack is not particularly limited. For example, the battery protective layer can be compounded with the body material and then placed above the single battery top cover assembly, preferably between the single battery top cover assembly and the upper cover of the battery module; the battery protective layer may also be directly combined with a structural component in the battery pack, such as a battery module upper cover, a battery module wire harness isolation plate, a battery pack upper cover, and the like, and specifically, the battery protective layer may be disposed on an inner side of the battery module upper cover, an inner side of the battery module wire harness isolation plate, or an inner side of the battery pack upper cover. The battery protection layer can be arranged at one position in the battery pack, and can also be arranged at a plurality of positions in the battery pack at the same time. Like this, thermal runaway appears in a certain battery cell, the inside active material granule of battery cell sprays out the back from the explosion-proof mouth of top cap subassembly with the form of spark, the battery inoxidizing coating that sets up in the battery package can bear the explosion impact well and separation spark, prevent effectively that the battery package upper cover from being directly strikeed by spark, delay or prevent that the battery package upper cover is decomposed or melt in the short time, the battery inoxidizing coating that sets up in the battery package simultaneously can also restrain the combustion diffusion, even make it from putting out, finally effectively avoid the battery package to catch fire or explode, the security in the improvement battery package use. In addition, the battery inoxidizing coating of battery cell top cap subassembly top position can also play the effect of avoiding the condition of a fire to spread to other battery cells, and the battery inoxidizing coating of battery module upper cover and battery module pencil division board inboard position can also play the effect of avoiding the condition of a fire to spread to other battery modules in the battery package.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In the following specific examples, the reagents used are commercially available, unless otherwise specified.
Example 1
Dissolving 40 parts by mass of organic silicon modified epoxy resin in acetone, then adding 25 parts by mass of glass fiber reinforced filler and 10 parts by mass of phosphate flame retardant, uniformly mixing, then adding 0.5 part by mass of silane coupling agent gamma-aminopropyltriethoxysilane, uniformly mixing again, then adding 25 parts by mass of imidazole curing agent, and uniformly stirring to obtain a mixed solution; and brushing the mixed solution on the surface of the glass fiber cloth, fully soaking the glass fiber cloth in the mixed solution, covering the glass fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 80 ℃ for 2 hours to form a battery protective layer with the thickness of 2 mm.
Example 2
Dissolving 80 parts by mass of phenolic aldehyde modified epoxy resin into diethylene glycol monomethyl ether, then adding 40 parts by mass of carbon fiber reinforced filler and 25 parts by mass of ammonium polyphosphate flame retardant, uniformly mixing, then adding 1 part by mass of silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, uniformly mixing again, then adding 40 parts by mass of anhydride curing agent, and uniformly stirring to obtain a mixed solution; brushing the mixed solution on the surface of the basalt fiber cloth, fully soaking the basalt fiber cloth in the mixed solution, covering the basalt fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 100 ℃ for 6 hours to form a battery protective layer with the thickness of 2 mm.
Example 3
Dissolving 60 parts by mass of maleimide modified epoxy resin in ethyl acetate, then adding 60 parts by mass of basalt fiber reinforced filler and 25 parts by mass of phosphate flame retardant, uniformly mixing, then adding 2 parts by mass of silane coupling agent gamma-methacryloxypropyltrimethoxysilane, uniformly mixing again, then adding 30 parts by mass of polyamide curing agent, and uniformly stirring to obtain a mixed solution; spraying the mixed solution on the surface of the acrylic cotton fiber cloth, fully soaking the acrylic cotton fiber cloth in the mixed solution, covering the acrylic cotton fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 25 ℃ for 6 hours to form a battery protective layer with the thickness of 2 mm.
Example 4
Dissolving 80 parts by mass of benzoxazine-modified epoxy resin in butanone, then adding 60 parts by mass of quartz fiber reinforced filler and 40 parts by mass of phosphite flame retardant, uniformly mixing, then adding 2 parts by mass of silane coupling agent gamma-mercaptopropyl trimethoxysilane, uniformly mixing again, adding 40 parts by mass of boron trifluoride complex curing agent, and uniformly stirring to obtain a mixed solution; and spraying the mixed solution on the surface of the carbon fiber cloth, fully soaking the carbon fiber cloth in the mixed solution, covering the carbon fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 100 ℃ for 4 hours to form a battery protective layer with the thickness of 2 mm.
Example 5
Dissolving 40 parts by mass of organic silicon modified epoxy resin in ethyl acetate, then adding 60 parts by mass of basalt fiber reinforced filler and 10 parts by mass of phosphate flame retardant, uniformly mixing, then adding 2 parts by mass of silane coupling agent gamma-methacryloxypropyltrimethoxysilane, uniformly mixing again, then adding 25 parts by mass of imidazole curing agent, and uniformly stirring to obtain a mixed solution; and brushing the mixed solution on the surface of the glass fiber cloth, fully soaking the glass fiber cloth in the mixed solution, covering the glass fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 80 ℃ for 4 hours to form a battery protective layer with the thickness of 0.2 mm.
Example 6
Dissolving 60 parts by mass of maleimide modified epoxy resin in butanone, then adding 60 parts by mass of carbon fiber reinforced filler and 5 parts by mass of phosphite flame retardant, uniformly mixing, then adding 1 part by mass of silane coupling agent gamma-aminopropyltriethoxysilane, uniformly mixing again, then adding 30 parts by mass of polyamide curing agent, and uniformly stirring to obtain a mixed solution; brushing the mixed solution on the surface of the basalt fiber cloth, fully soaking the basalt fiber cloth in the mixed solution, covering the basalt fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 25 ℃ for 4 hours to form a battery protective layer with the thickness of 0.5 mm.
Example 7
Dissolving 60 parts by mass of phenolic aldehyde modified epoxy resin in diethylene glycol monomethyl ether, then adding 40 parts by mass of quartz fiber reinforced filler and 40 parts by mass of phosphate flame retardant, uniformly mixing, then adding 1.5 parts by mass of silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, uniformly mixing again, then adding 30 parts by mass of anhydride curing agent, and uniformly stirring to obtain a mixed solution; and spraying the mixed solution on the surface of the glass fiber cloth, fully soaking the glass fiber cloth in the mixed solution, covering the glass fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 100 ℃ for 6 hours to form a battery protective layer with the thickness of 1.5 mm.
Example 8
Dissolving 80 parts by mass of benzoxazine-modified epoxy resin in ethyl acetate, adding 40 parts by mass of glass fiber reinforced filler and 5 parts by mass of ammonium polyphosphate flame retardant, uniformly mixing, adding 1.5 parts by mass of silane coupling agent gamma-mercaptopropyl-trimethoxysilane, uniformly mixing again, adding 30 parts by mass of imidazole curing agent, and uniformly stirring to obtain a mixed solution; spraying the mixed solution on the surface of the acrylic cotton fiber cloth, fully soaking the acrylic cotton fiber cloth in the mixed solution, covering the acrylic cotton fiber cloth on the inner side of the upper cover of the battery pack, and heating and curing at 80 ℃ for 6 hours to form a battery protective layer with the thickness of 3 mm.
Comparative example 1
The battery pack upper cover is not protected.
Next, a test procedure of the battery pack is explained.
And (3) puncturing the single batteries from the direction vertical to the front surface of the battery pack at the speed of 80mm/s by adopting a high-temperature-resistant steel needle with the diameter of 3mm, so that the outermost single batteries are subjected to thermal runaway, observing the state of the battery pack, and recording the fusion time of the upper cover of the battery pack and the surface temperature of the battery pack.
TABLE 1 test results of examples 1-8 and comparative example 1
From the test result, when certain battery cell of battery package inside takes place the thermal runaway, the inboard battery inoxidizing coating of battery package upper cover has the effect that bears the explosion impact, separation spark and suppression combustion diffusion, can prevent effectively that the battery package upper cover is directly strikeed by spark, effectively delays or stops the battery package upper cover and is decomposed or melt in the short time, avoids taking place the thermal diffusion of large tracts of land, and the security of greatly improving the battery package avoids appearing catching a fire or exploding.
Comparative example 1 no battery protection layer was provided at the inner side of the upper cover of the battery pack, when thermal runaway occurred in a certain single battery inside the battery pack, active material particles inside the single battery were ejected from the explosion-proof port in the form of sparks and directly impacted the upper cover of the battery pack, so that the upper cover of the battery pack was melted through in a short time (e.g., within 1 s), and the fire was gradually diffused to other single batteries or other battery modules inside the battery pack, and large-area thermal diffusion occurred, which seriously affected the use of the battery pack.
Claims (10)
1. The battery protective layer is characterized by comprising a fireproof cloth and a functional layer arranged on the fireproof cloth, wherein the functional layer is a thermosetting resin layer mainly formed by curing an epoxy resin matrix, an epoxy resin curing agent, a reinforcing filler, a flame retardant and a silane coupling agent.
2. The battery armor layer of claim 1, wherein the functional layer comprises:
40-80 parts by mass of an epoxy resin matrix;
20-40 parts by mass of an epoxy resin curing agent;
20-60 parts by mass of a reinforcing filler;
5-40 parts by mass of a flame retardant;
0.5-2 parts by mass of a silane coupling agent.
3. The battery protection layer according to claim 1 or 2,
the epoxy resin matrix is selected from one or more of organic silicon modified epoxy resin, phenolic aldehyde modified epoxy resin, maleimide modified epoxy resin and benzoxazine modified epoxy resin;
the epoxy resin curing agent is selected from one or more of imidazoles, acid anhydrides, polyamides, tertiary amines, boron trifluoride and complexes thereof;
the reinforcing filler is selected from one or more of glass fiber, carbon fiber, basalt fiber, quartz fiber and asbestos fiber;
the flame retardant is a phosphorus-containing flame retardant, preferably one or more selected from phosphate, ammonium polyphosphate, phosphate and phosphite;
the silane coupling agent is selected from one or more of gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, gamma-mercaptopropyl trimethoxysilane and gamma-mercaptopropyl triethoxysilane.
4. The battery protection layer according to claim 1, wherein the fireproof cloth is selected from one or more of glass fiber cloth, basalt fiber cloth, acrylic cotton fiber cloth and carbon fiber cloth.
5. The battery protective layer according to claim 3, wherein the curing temperature of the epoxy resin curing agent is 25 ℃ to 100 ℃.
6. The battery protection layer of claim 1, wherein the thickness of the battery protection layer is 0.5mm to 3 mm.
7. A method for preparing a battery protection layer, for preparing the battery protection layer of any one of claims 1 to 6, comprising the steps of:
dissolving an epoxy resin matrix in a solvent to obtain an epoxy resin matrix solution;
then adding the reinforcing filler and the flame retardant into the epoxy resin matrix solution, uniformly mixing, then adding the silane coupling agent, uniformly mixing again, adding the epoxy resin curing agent, and uniformly stirring to obtain a mixed solution;
and fully soaking the mixed solution into the fireproof cloth, then covering the fireproof cloth on the body material, standing at room temperature or heating to cure the epoxy resin matrix in the mixed solution to form a thermal curing resin layer, and finishing the preparation of the battery protective layer.
8. Use of the battery protective layer according to any one of claims 1 to 6 in a battery module or a battery pack.
9. The use of claim 8, wherein the battery protection layer is disposed at a position above a top cap assembly of the single battery inside the battery module or the battery pack.
10. The use according to claim 8, wherein the battery protection layer is arranged at one or more of the inner side of the battery module upper cover, the inner side of the battery module harness isolation plate and the inner side of the battery pack upper cover.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN114953624A (en) * | 2022-05-28 | 2022-08-30 | 安徽天富环保科技材料有限公司 | Activated carbon fiber cloth for preparing new energy battery |
| CN115302893A (en) * | 2022-08-29 | 2022-11-08 | 浙江葆润应用材料有限公司 | Double-layer laminated flame-retardant material for battery pack and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605837A (en) * | 2022-03-10 | 2022-06-10 | 浙江葆润应用材料有限公司 | Integrally-formed fireproof PCM composite material for battery pack and preparation method thereof |
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| CN114953624A (en) * | 2022-05-28 | 2022-08-30 | 安徽天富环保科技材料有限公司 | Activated carbon fiber cloth for preparing new energy battery |
| CN114953624B (en) * | 2022-05-28 | 2023-09-15 | 安徽天富环保科技材料有限公司 | Active carbon fiber cloth for preparing new energy battery |
| CN115302893A (en) * | 2022-08-29 | 2022-11-08 | 浙江葆润应用材料有限公司 | Double-layer laminated flame-retardant material for battery pack and preparation method thereof |
| CN115302893B (en) * | 2022-08-29 | 2024-03-08 | 浙江葆润应用材料有限公司 | Double-layer laminated flame-retardant material for battery pack and preparation method thereof |
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