CN116144164A - Battery swelling membrane and preparation method and application thereof - Google Patents

Battery swelling membrane and preparation method and application thereof Download PDF

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Publication number
CN116144164A
CN116144164A CN202211676797.8A CN202211676797A CN116144164A CN 116144164 A CN116144164 A CN 116144164A CN 202211676797 A CN202211676797 A CN 202211676797A CN 116144164 A CN116144164 A CN 116144164A
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component
hardness
parts
weight
battery swelling
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何建雄
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Dongguan Xionglin New Materials Technology Co Ltd
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Dongguan Xionglin New Materials Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • 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
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/08—Polyurethanes from polyethers
    • 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

Abstract

The invention provides a battery swelling film and a preparation method and application thereof, wherein the material of the battery swelling film comprises a high-hardness TPU, a low-hardness TPU and an anhydride grafting agent, the preparation raw materials of the high-hardness TPU comprise a component A and a component B, the component A comprises polyester polyol and small molecular dihydric alcohol with a branched structure, the component B comprises diphenylmethane diisocyanate curing agent, the preparation raw materials of the low-hardness TPU comprise a component C and a component D, the component C comprises polyether type linear dihydric alcohol and small molecular linear dihydric alcohol, and the component D comprises toluene diisocyanate curing agent; the TPU with the two hardness is selected for matching, and meanwhile, the anhydride grafting agent is added, so that the battery swelling film with good swelling multiplying power, excellent bonding performance and high temperature resistance is obtained.

Description

Battery swelling membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water treatment of lithium ion batteries, and particularly relates to a battery swelling membrane, a preparation method and application thereof.
Background
At present, the manufacturing process of the lithium ion battery has been developed and widely applied in production. Because there is certain space between electric core and the cylindrical shell when the cylindrical battery is assembled, if the electric core can not be effectively fixed in the shell, after vibration or external impact occurs, the problems of electrode plate damage, battery short circuit, resistance increase and the like caused by the relative movement of the bare electric core and the shell of the lithium battery are very easy to occur, thereby influencing the service performance of the lithium battery and also causing great potential safety hazard. Therefore, it is necessary to bond the bare cell and the cylindrical case and fill the gap between them.
TPU is increasingly popular due to its superior performance and environmental protection concept, and TPU not only has excellent high tension, toughness and aging resistance, but also is a mature environmental protection material, and at present, TPU has been widely applied to: shoe materials, ready-made clothes, inflatable toys, sports equipment on water and under water, medical equipment, fitness equipment, automobile seat materials, umbrellas, leather cases, leather bags and the like. CN111518481a discloses a swelling adhesive tape special for lithium battery and a manufacturing process thereof, comprising a substrate layer and a coated pressure-sensitive adhesive layer, wherein substances such as TPU particles, EVA particles, a styrene resin solution, a (titanium white) pigment and the like are added in the manufacturing process of the substrate layer, so that the substrate layer still keeps higher area swelling when electrolyte is reduced or removed, the pressure-sensitive adhesive layer is insoluble after being soaked in the electrolyte, and still has viscosity in the electrolyte environment, and the swelling adhesive tape special for lithium battery prepared by the process can be swelled and deformed in the length-width direction after the swelling adhesive tape special for lithium battery contacts with the electrolyte of lithium ion battery, and the area is increased to more than 200% of the original area; however, this technique can only achieve swelling deformation of the adhesive tape in the length-width direction to form a folded filling gap, but it cannot fill the void in the cylindrical battery in all directions.
CN111995957a discloses an oriented polystyrene expansion adhesive tape and a preparation method thereof, wherein the adhesive tape is formed by compounding an oriented polystyrene film base material with a single-sided release layer and an acrylic ester adhesive layer, and the expansion ratio of the adhesive tape in the thickness direction is 400%, but the adhesive tape has low temperature resistance and cannot be used due to high-temperature shrinkage.
Therefore, it is an urgent technical problem in the art to provide a swelling film for a battery capable of swelling at a high rate in an area in an electrolyte and having excellent adhesive property and high temperature resistance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a battery swelling membrane, a preparation method and application thereof, wherein the material of the battery swelling membrane comprises high-hardness TPU, low-hardness TPU and anhydride grafting agent, the TPU with the two hardness is selected for matching, and the anhydride grafting agent is added at the same time, so that the area of the obtained battery swelling membrane in electrolyte can be expanded at a high rate, and the battery swelling membrane has excellent bonding performance and high temperature resistance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a battery swelling membrane, the material of which comprises a high hardness TPU, a low hardness TPU and an anhydride grafting agent;
the preparation raw materials of the high-hardness TPU comprise an A component and a B component, wherein the A component comprises polyester polyol and small molecular dihydric alcohol with a branched structure, and the B component comprises diphenylmethane diisocyanate curing agent;
the preparation raw materials of the low-hardness TPU comprise a C component and a D component, wherein the C component comprises polyether type linear dihydric alcohol and small molecular linear dihydric alcohol, and the D component comprises toluene diisocyanate curing agent;
the hardness of the high hardness TPU is higher than the hardness of the low hardness TPU.
The material of the battery swelling film comprises a high-hardness TPU, a low-hardness TPU and an anhydride grafting agent, wherein the preparation raw materials of the high-hardness TPU comprise an A component and a B component, the A component comprises polyester polyol and micromolecular dihydric alcohol with a branched structure, the B component comprises diphenylmethane diisocyanate curing agent, the preparation raw materials of the low-hardness TPU comprise a C component and a D component, the C component comprises polyether type linear dihydric alcohol and micromolecular linear dihydric alcohol, and the D component comprises toluene diisocyanate curing agent; the TPU with two types of hardness is selected for matching, and meanwhile, the anhydride grafting agent is added, so that the obtained battery swelling film can fully absorb the solvent in the electrolyte to present a better swelling ratio, and has excellent bonding performance and high temperature resistance.
Preferably, the high hardness TPU has a hardness of 95A to 64D, for example 100A, 45D, 50D, 55D, 60D, or the like.
Preferably, the component A comprises the following components in parts by weight:
20 to 75 parts by weight of polyester polyol
5-20 parts by weight of small molecular dihydric alcohol with a branched structure.
As a preferable technical scheme of the invention, the polyester polyol and the micromolecular dihydric alcohol with a branched structure are selected to match in a specific dosage range, so that the prepared TPU has higher hardness.
Wherein the polyester polyol may be 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, or the like.
The small molecular diol having a branched structure may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, or the like.
Preferably, the mass ratio of the A component and the B component is 1 (0.02-0.5), such as 1:0.05, 1:0.07, 1:0.09, 1:0.11, 1:0.13, 1:0.17, 1:0.2, 1:0.23, 1:0.28, 1:0.31, 1:0.38, 1:0.43, 1:0.48, etc.
Preferably, the small molecular diol with a branched structure comprises any one or a combination of at least two of 1, 2-propanediol, methylpropanediol, 1, 3-butanediol or neopentyl glycol.
Preferably, the polyester polyol comprises a polyester diol.
Preferably, the polyester diol comprises any one or a combination of at least two of polyethylene adipate glycol, polybutylene adipate glycol, polyethylene/butylene adipate glycol, polyhexamethylene adipate glycol, or polytetrahydrofuran glycol.
Preferably, the hardness of the low hardness TPU is 70 to 85A, for example 72A, 74A, 76A, 78A, 70A, 71A, 72A, 73A, 74A, or the like.
Preferably, the component C comprises the following components in parts by weight:
5 to 20 parts by weight of polyether type straight chain dihydric alcohol
5-10 parts by weight of small molecular straight-chain dihydric alcohol.
As the preferable technical scheme of the invention, polyether type linear dihydric alcohol and small molecular linear dihydric alcohol are selected to match within the specific dosage range, so that the obtained TPU has lower hardness.
Wherein the polyether type linear diol may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, or the like.
The small molecular straight chain dihydric alcohol may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, or the like.
Preferably, the mass ratio of the C component and the D component is 1 (0.02-0.5), such as 1:0.05, 1:0.07, 1:0.09, 1:0.11, 1:0.13, 1:0.17, 1:0.2, 1:0.23, 1:0.28, 1:0.31, 1:0.38, 1:0.43, 1:0.48, etc.
Preferably, the polyether linear diol comprises polypropylene glycol and/or polytetrahydrofuran diol.
Preferably, the small molecule linear diol comprises ethylene glycol and/or propylene glycol.
Preferably, the anhydride grafting agent comprises POE grafted maleic anhydride.
Preferably, the materials of the battery swelling film comprise the following components in parts by weight:
10 to 50 parts by weight of high-hardness TPU
10 to 50 parts by weight of low-hardness TPU
5-20 parts of anhydride grafting agent.
Wherein the high hardness TPU may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
The low hardness TPU may be 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
The acid anhydride grafting agent may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 15 parts by weight, 17 parts by weight, 19 parts by weight, 19.5 parts by weight, 20 parts by weight, or the like.
Preferably, the material of the battery swelling film further comprises a thermal cross-linking agent.
Preferably, the thermal crosslinking agent comprises an organic peroxide and/or diethylenetriamine.
Preferably, the content of the thermal crosslinking agent in the material of the battery swelling film is 1 to 5 parts by weight, for example, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or the like.
In a second aspect, the present invention provides a method for producing a battery swelling film according to the first aspect, the method comprising the steps of:
(1) Reacting the component A and the component B in the high-hardness TPU to obtain the high-hardness TPU; reacting the C component and the D component in low hardness to obtain high-hardness TPU;
(2) And (3) introducing the high-hardness TPU, the low-hardness TPU, the anhydride grafting agent and the optional thermal crosslinking agent obtained in the step (1) into a double-screw extruder to obtain a molten colloid, and then casting and molding the molten colloid to obtain the battery swelling film.
In a third aspect, the present invention provides the use of a battery swelling membrane according to the first aspect in a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) The material of the battery swelling film provided by the invention comprises high-hardness TPU, low-hardness TPU and anhydride grafting agent; the preparation raw materials of the high-hardness TPU comprise an A component and a B component, wherein the A component comprises polyester polyol and micromolecular dihydric alcohol with a branched structure, and the B component comprises isocyanate curing agent; the preparation raw materials of the low-hardness TPU comprise a C component and a D component, wherein the C component comprises polyether type linear dihydric alcohol and small molecular linear dihydric alcohol, and the D component comprises isocyanate prepolymer curing agent; the hardness of the high-hardness TPU is higher than that of the low-hardness TPU; the TPU with the two hardness and the anhydride grafting agent are selected, the preparation raw materials of the TPU with the two hardness are limited, and the TPU with the two hardness are selected for matching, and the anhydride grafting agent is added at the same time, so that the obtained battery swelling film can fully absorb the solvent in the electrolyte to show good swelling multiplying power, and has excellent bonding performance and high temperature resistance.
(2) Specifically, the peeling force of the battery swelling film provided by the invention is 1.45-1.55N/25 mm, the swelling rate at 45 ℃ is 173-184%, and the swelling rate at 85 ℃ is 198-208%.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The battery swelling film comprises the following materials in parts by weight:
Figure BDA0004017277150000061
wherein the hardness of the high-hardness TPU is 50D, the preparation raw materials of the high-hardness TPU comprise an A component and a B component in a mass ratio of 1:0.25, the A component comprises 30 parts by weight of polyethylene glycol adipate glycol (with a molecular weight of 2000) and 10 parts by weight of 1, 2-propylene glycol, and the B component comprises diphenylmethane diisocyanate curing agent;
the low-hardness TPU has the hardness of 80A, and is prepared from a C component and a D component in a mass ratio of 1:0.25, wherein the C component comprises 10 parts by weight of polypropylene glycol (with a molecular weight of 2000) and 5 parts by weight of ethylene glycol, and the D component is prepared from a toluene diisocyanate curing agent;
the preparation method of the battery swelling film provided by the embodiment comprises the following steps:
(1) Feeding polyethylene glycol adipate glycol, 1, 2-propylene glycol and diphenylmethane diisocyanate curing agent into a double screw extruder for only extrusion, and setting the extrusion temperature to 200 ℃ to obtain high-hardness TPU; feeding polypropylene glycol, ethylene glycol and toluene diisocyanate curing agent into a double-screw extruder for only extrusion, and setting the extrusion temperature to 120 ℃ to obtain low-hardness TPU;
(2) And (3) introducing the high-hardness TPU, the low-hardness TPU, the POE grafted maleic anhydride and the diethylenetriamine obtained in the step (1) into a double-screw extruder to obtain molten colloid, and then carrying out casting molding on the molten colloid to obtain the battery swelling film.
Example 2
The battery swelling film comprises the following materials in parts by weight:
Figure BDA0004017277150000071
wherein the high-hardness TPU has a hardness of 95A, and the preparation raw materials comprise an A component and a B component in a mass ratio of 1:0.05, wherein the A component comprises 20 parts by weight of polyethylene glycol adipate glycol (with a molecular weight of 2000) and 5 parts by weight of 1, 2-propylene glycol, and the B component comprises diphenylmethane diisocyanate;
the low-hardness TPU has the hardness of 70A, and is prepared from a C component and a D component in a mass ratio of 1:0.05, wherein the C component comprises 5 parts by weight of polypropylene glycol (with a molecular weight of 2000) and 5 parts by weight of ethylene glycol, and the D component is prepared from a toluene diisocyanate curing agent;
the preparation method of the battery swelling film provided in this example is the same as that of example 1.
Example 3
The battery swelling film comprises the following materials in parts by weight:
Figure BDA0004017277150000081
wherein the hardness of the high-hardness TPU is 64D, the preparation raw materials of the high-hardness TPU comprise an A component and a B component in a mass ratio of 1:0.5, the A component comprises 75 parts by weight of polyethylene glycol adipate glycol (with a molecular weight of 2000) and 20 parts by weight of 1, 2-propylene glycol, and the B component comprises diphenylmethane diisocyanate;
the low-hardness TPU has the hardness of 85A, and is prepared from a C component and a D component in a mass ratio of 1:0.5, wherein the C component comprises 20 parts by weight of polypropylene glycol (with a molecular weight of 2000) and 20 parts by weight of ethylene glycol, and the D component is prepared from a toluene diisocyanate curing agent;
the preparation method of the battery swelling film provided in this example is the same as that of example 1.
Example 4
A battery swelling film differing from example 1 only in that a polybutylene adipate glycol having a molecular weight of 2000 was used instead of a polyethylene adipate glycol having a molecular weight of 2000, and the other components, amounts and preparation methods were the same as in example 1.
Example 5
A battery swelling film differing from example 1 only in that a polytetrahydrofuran diol having a molecular weight of 2000 was used instead of a polypropylene glycol having a molecular weight of 2000, and the other components, amounts and preparation methods were the same as in example 1.
Example 6
A battery swelling film was different from example 1 only in that diethylenetriamine was not added, and other components, amounts and preparation methods were the same as those of example 1.
Comparative example 1
The battery swelling film comprises the following materials in parts by weight:
50 parts by weight of high-hardness TPU
13 parts by weight of anhydride grafting agent
2.5 parts by weight of diethylenetriamine;
wherein the hardness of the high-hardness TPU is 50D, the preparation raw materials of the high-hardness TPU comprise an A component and a B component in a mass ratio of 1:0.25, the A component comprises 30 parts by weight of polyethylene glycol adipate glycol (with a molecular weight of 2000) and 10 parts by weight of 1, 2-propylene glycol, and the B component comprises diphenylmethane diisocyanate curing agent;
the preparation method of the battery swelling film provided by the embodiment comprises the following steps:
(1) Feeding polyethylene glycol adipate glycol, 1, 2-propylene glycol and diphenylmethane diisocyanate curing agent into a double screw extruder for only extrusion, and setting the extrusion temperature to 200 ℃ to obtain high-hardness TPU;
(2) And (3) introducing the high-hardness TPU, POE grafted maleic anhydride and diethylenetriamine obtained in the step (1) into a double-screw extruder to obtain molten colloid, and then carrying out casting molding on the molten colloid to obtain the battery swelling film.
Comparative example 2
The battery swelling film comprises the following materials in parts by weight:
50 parts by weight of low-hardness TPU
13 parts by weight of anhydride grafting agent
2.5 parts by weight of diethylenetriamine;
wherein the hardness of the low-hardness TPU is 80A, the preparation raw materials comprise a C component and a D component in a mass ratio of 1:0.25, the C component comprises 10 parts by weight of polypropylene glycol (with a molecular weight of 2000) and 5 parts by weight of ethylene glycol, and the preparation raw materials of the D component comprise toluene diisocyanate curing agent;
the preparation method of the battery swelling film provided by the embodiment comprises the following steps:
(1) Feeding polypropylene glycol, ethylene glycol and toluene diisocyanate curing agent into a double-screw extruder for only extrusion, and setting the extrusion temperature to 120 ℃ to obtain low-hardness TPU;
(2) And (3) introducing the low-hardness TPU, POE grafted maleic anhydride and diethylenetriamine obtained in the step (1) into a double-screw extruder to obtain molten colloid, and then carrying out casting molding on the molten colloid to obtain the battery swelling film.
Comparative example 3
A battery swelling film was different from example 1 only in that diethylenetriamine was not added, and other components, amounts and preparation methods were the same as those of example 1.
Performance test:
(1) Adhesive properties: the test method of the stripping force of the steel plate refers to the standard GB/T2792-2014;
(2) Swelling ratio: total thickness h of reference standard test sample GB/T7125-2014 0 Cutting a test sample into 5 pieces with the size of 50X 50mm, placing the cut adhesive tape into a PE bottle, pouring electrolyte, respectively baking at 45 ℃ and 85 ℃ for 36 hours after the sample is taken out, flattening the sample, testing the length a and the width b (the shrinkage in the length-width direction is less than or equal to 10 percent) of the sample by a 30cm steel rule, and referring to the thickness h of the baked sample soaked in the electrolyte according to the standard test of GB/T7125-2014 1 Swelling ratio=h 1 /h 0 ×100％。
The battery swelling films provided in examples 1 to 6 and comparative examples 1 to 3 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
Peel force/N/25 mm Swelling ratio at 45 ℃/% Swelling ratio at 85 ℃/%
Example 1 1.55 182 208
Example 2 1.45 184 207
Example 3 1.55 183 204
Example 4 1.5 179 202
Example 5 1.55 173 201
Example 6 1.5 178 198
Comparative example 1 1.35 110 135
Comparative example 2 1.25 120 Dissolving
Comparative example 3 1.45 98 107
As can be seen from the data in table 1, the battery swelling film provided by the invention has excellent adhesive property, higher swelling rate and excellent high temperature resistance.
Specifically, examples 1 to 6 provided battery swelling films having a peel force of 1.45 to 1.55N/25mm, a swelling ratio at 45℃of 173 to 184%, and a swelling ratio at 85℃of 198 to 208%.
As can be seen from comparing the data of example 1 and comparative example 1, the peeling force of the battery swelling film containing only the high-hardness TPU was low and the swelling ratio in the electrolyte was low.
As can also be seen from comparing the data of example 1 and comparative example 2, the peel force of the battery swelling film containing only the low hardness TPU is also lower and the high temperature resistance is inferior.
Further comparing the data of example 1 and comparative example 3, it can also be seen that the swelling properties of the battery swelling film are affected without the addition of an anhydride grafting agent.
Finally, comparing the data of example 1 and example 6, it can also be seen that the addition of the thermal crosslinking agent also affects the swelling properties of the battery swelling film.
The applicant states that the present invention is described by way of the above examples as a battery swelling film and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (10)

1. A battery swelling membrane, characterized in that the material of the battery swelling membrane comprises high-hardness TPU, low-hardness TPU and anhydride grafting agent;
the preparation raw materials of the high-hardness TPU comprise an A component and a B component, wherein the A component comprises polyester polyol and small molecular dihydric alcohol with a branched structure, and the B component comprises diphenylmethane diisocyanate curing agent;
the preparation raw materials of the low-hardness TPU comprise a C component and a D component, wherein the C component comprises polyether type linear dihydric alcohol and small molecular linear dihydric alcohol, and the D component comprises toluene diisocyanate curing agent;
the hardness of the high hardness TPU is higher than the hardness of the low hardness TPU.
2. The battery swelling film of claim 1, wherein the high hardness TPU has a hardness of 95A to 64D;
preferably, the component A comprises the following components in parts by weight:
20 to 75 parts by weight of polyester polyol
5-20 parts by weight of small molecular dihydric alcohol with a branched structure.
3. The battery swelling film according to claim 1 or 2, wherein the mass ratio of the a component to the B component is 1 (0.02 to 0.5).
4. The battery swelling film of any of claims 1 to 3, wherein the small-molecule diol having a branched structure comprises any one or a combination of at least two of 1, 2-propanediol, methylpropanediol, 1, 3-butanediol, or neopentyl glycol;
preferably, the polyester polyol comprises a polyester diol;
preferably, the polyester diol comprises any one or a combination of at least two of polyethylene adipate glycol, polybutylene adipate glycol, polyethylene/butylene adipate glycol, polyhexamethylene adipate glycol, or polytetrahydrofuran glycol.
5. The battery swelling film of any of claims 1 to 4, wherein the low hardness TPU has a hardness of 70 to 85A;
preferably, the component C comprises the following components in parts by weight:
5 to 20 parts by weight of polyether type straight chain dihydric alcohol
5-10 parts by weight of small molecular straight-chain dihydric alcohol;
preferably, the polyether type linear diol comprises polypropylene glycol and/or polytetrahydrofuran diol;
preferably, the small molecule linear diol comprises ethylene glycol and/or propylene glycol.
6. The battery swelling film according to any one of claims 1 to 5, wherein the mass ratio of the C component and the D component is 1 (0.02 to 0.5).
7. The battery swelling membrane of any of claims 1 to 6, wherein the anhydride grafting agent comprises POE grafted maleic anhydride;
preferably, the materials of the battery swelling film comprise the following components in parts by weight:
10 to 50 parts by weight of high-hardness TPU
10 to 50 parts by weight of low-hardness TPU
5-20 parts of anhydride grafting agent.
8. The battery swelling membrane of any of claims 1 to 7, wherein the material of the battery swelling membrane further comprises a thermal cross-linking agent;
preferably, the thermal crosslinking agent comprises an organic peroxide and/or diethylenetriamine;
preferably, the content of the thermal crosslinking agent in the material of the battery swelling film is 1 to 5 parts by weight.
9. A method for producing the battery swelling film according to any one of claims 1 to 8, comprising the steps of:
(1) Reacting the component A and the component B in the high-hardness TPU to obtain the high-hardness TPU; reacting the C component and the D component in low hardness to obtain high-hardness TPU;
(2) And (3) introducing the high-hardness TPU, the low-hardness TPU, the anhydride grafting agent and the optional thermal crosslinking agent obtained in the step (1) into a double-screw extruder to obtain a molten colloid, and then casting and molding the molten colloid to obtain the battery swelling film.
10. Use of a battery swelling membrane according to any one of claims 1 to 8 in a lithium ion battery.
CN202211676797.8A 2022-12-26 2022-12-26 Battery swelling membrane and preparation method and application thereof Pending CN116144164A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211676797.8A CN116144164A (en) 2022-12-26 2022-12-26 Battery swelling membrane and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211676797.8A CN116144164A (en) 2022-12-26 2022-12-26 Battery swelling membrane and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116144164A true CN116144164A (en) 2023-05-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211676797.8A Pending CN116144164A (en) 2022-12-26 2022-12-26 Battery swelling membrane and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116144164A (en)

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