CN117903711A - Blue insulating tape applied to lithium battery and manufacturing method thereof - Google Patents

Blue insulating tape applied to lithium battery and manufacturing method thereof Download PDF

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Publication number
CN117903711A
CN117903711A CN202410007574.5A CN202410007574A CN117903711A CN 117903711 A CN117903711 A CN 117903711A CN 202410007574 A CN202410007574 A CN 202410007574A CN 117903711 A CN117903711 A CN 117903711A
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lithium battery
parts
substrate layer
insulating tape
blue
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CN117903711B (en
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林锦鑫
陈国德
张术锐
胡永红
周钰萍
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Jiangxi Xinmei New Material Technology Co ltd
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Jiangxi Xinmei New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04—Alginic acid; Derivatives thereof
    • 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
    • C08J2451/04—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 rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

The invention relates to the technical field of adhesive tapes for lithium batteries, and discloses a blue insulating adhesive tape applied to a lithium battery and a manufacturing method thereof, wherein the insulating adhesive tape comprises a substrate layer, a release layer and an adhesive layer; wherein the substrate layer comprises the following raw materials: PET resin, filler, coupling agent, antioxidant and pigment; the flame retardant also comprises a heat-stable toughening agent and a synergistic flame retardant compound; wherein the heat-stable toughening agent is a rubber toughening agent containing a rigid ring in the structure; the synergistic flame-retardant compound is a macromolecular flame retardant containing nitrogen and phosphorus, and the insulating adhesive tape prepared by the invention has excellent thermal stability and flame-retardant capability, reduces the influence on the adhesive tape for the lithium battery in a high-temperature environment, can rapidly play a flame-retardant role when the lithium battery is in a fire disaster, delays the spreading speed of the fire, protects surrounding electronic elements, and prolongs the service life and safety of the lithium battery.

Description

Blue insulating tape applied to lithium battery and manufacturing method thereof
Technical Field
The invention relates to the technical field of adhesive tapes for lithium batteries, in particular to a blue insulating adhesive tape applied to a lithium battery and a manufacturing method thereof.
Background
With the popularization of mobile equipment and the development of electric vehicles, a lithium battery is widely focused as an efficient energy storage device, in the manufacturing process of the lithium battery, an adhesive tape plays an important role in fixing an internal component, in view of the working specificity of the lithium battery, the adhesive tape for the lithium battery is generally required to have excellent thermal stability and flame retardant property so as to prevent the adhesive tape from deforming and losing viscosity caused by a high-temperature and high-heat environment generated during the working of the lithium battery, thereby damaging the adhesive tape, generating the risks of fixing loosening, shifting and even falling off of electronic elements, influencing the working safety of the lithium battery, reducing the service life of the lithium battery, and in the case of improper use and abnormal performance of the lithium battery, the burning phenomenon possibly occurs due to local overheating, and if the lithium battery adhesive tape has no flame retardant capability, the fire spreads too quickly to cause damage to surrounding electronic elements, thereby bringing great potential safety hazards while bringing about property loss.
However, the conventional lithium battery adhesive tape also has the problems of poor thermal stability and poor flame retardance, so that the development and application of a lithium battery are greatly limited, and based on the problems, the lithium battery adhesive tape is improved once and once to prolong the service life of the lithium battery, for example, the patent with the publication number of CN114539940B discloses a preparation method of a high-temperature-resistant lithium battery adhesive tape, and the patent participates in the preparation process of a substrate layer by using polyester and silicone oil, and meanwhile, the heat conduction performance and the insulation performance of the substrate layer are improved by adding hexagonal boron nitride, so that the prepared adhesive tape can have excellent thermal stability and heat conduction and insulation capabilities, but the flame retardance of the adhesive tape prepared by the patent is insufficient, and the risk of fire spreading during fire disaster occurs.
Disclosure of Invention
The invention aims to provide a blue insulating tape applied to a lithium battery and a manufacturing method thereof, which solve the following technical problems: (1) The traditional adhesive tape for the lithium battery has insufficient thermal stability, is easily influenced by heat generated in the charging process of the lithium battery, and causes the problem of service life reduction; (2) The traditional adhesive tape for the lithium battery has no flame retardant effect when the lithium battery knocks, and can not prevent the fire from spreading.
The aim of the invention can be achieved by the following technical scheme:
A blue insulating tape applied to a lithium battery comprises a substrate layer, a release layer and an adhesive layer; the release layer and the adhesive layer are distributed on two sides of the substrate layer; the substrate layer comprises the following raw materials in parts by weight: 50-80 parts of PET resin, 2-6 parts of filler, 2-5 parts of coupling agent, 3-5 parts of antioxidant and 1-3 parts of pigment; the substrate layer also comprises 10-15 parts of heat-stable toughening agent and 3-6 parts of synergistic flame-retardant compound; the thermal stabilizing toughening agent is prepared by reacting natural rubber with 5-norbornene-2-carboxylic acid; the synergistic flame-retardant compound is prepared by sequentially reacting sodium alginate with 2, 3-pyrazinedicarboxylic anhydride and diethyl hydroxymethylphosphonate.
Further, the filler is any one of nano silicon dioxide, nano montmorillonite, halloysite nanotube and nano diatomite; the coupling agent is any one of a silane coupling agent and a titanate coupling agent; the antioxidant is a hindered phenol antioxidant; the pigment is any one of phthalocyanine blue pigment and cobalt blue pigment.
Further, the preparation method of the heat-stable toughening agent comprises the following steps:
And (3) placing the natural rubber in toluene, fully stirring for 2-3 hours, adding 5-norbornene-2-carboxylic acid, adding an initiator, heating to 60-70 ℃, stirring for 5-8 hours, cooling to room temperature, and collecting a product to obtain the heat-stable toughening agent.
In the scheme, under the action of an initiator, double bonds in a natural rubber structure and double bonds in a 5-norbornene-2-carboxylic acid structure undergo free radical polymerization reaction to obtain a heat-stable toughening agent, a norbornene rigid ring structure is introduced into the structure of the natural rubber, so that the compatibility of the natural rubber and a PET matrix can be enhanced, the heat stability of the natural rubber is enhanced, the natural rubber is prevented from breaking due to molecular chain breakage during melt extrusion when being blended with the matrix, the natural rubber loses elasticity and mechanical properties, after being blended with a PET matrix material, the rigid ring structure in the structure can also delay the heat degradation process of the matrix, so that the structural integrity and performance stability of the PET matrix can be maintained even if the PET matrix is in a high-temperature environment for a long time, meanwhile, the flexible chain segment in the molecular chain can also effectively buffer and disperse stress, the impact energy can be obviously enhanced, the prepared adhesive tape has excellent mechanical properties and heat stability, and the service life of the adhesive tape can be obviously prolonged.
Further, the initiator is any one of azobisisobutyronitrile and azobisisoheptonitrile.
Further, the preparation method of the synergistic flame retardant composite comprises the following steps:
S1, placing sodium alginate in deionized water, fully stirring for 1-2 hours, adding sodium hydroxide, adjusting the pH to 8-9, adding 2, 3-pyrazinedianhydride, heating to 55-65 ℃ for reaction for 3-5 hours, and removing the solvent by rotary evaporation to obtain modified sodium alginate;
S2, placing the modified sodium alginate in N, N-dimethylformamide, adding the diethyl hydroxymethylphosphonate and the composite catalyst, heating to 50-60 ℃ for reaction for 24-48h, and collecting the product after the reaction is completed to obtain the synergistic flame-retardant compound.
In the scheme, hydroxy in the sodium alginate structure and anhydride groups in the 2, 3-pyrazinedicarboxylic anhydride structure undergo ring-opening reaction to obtain modified sodium alginate, carboxyl in the modified sodium alginate structure and hydroxy in the hydroxymethylphosphonic diethyl structure undergo esterification reaction under the action of a composite catalyst to obtain a synergistic flame retardant compound, the synergistic flame retardant compound takes sodium alginate as a carbonizing agent, 2, 3-pyrazinedicarboxylic anhydride as a nitrogen source and dimethylol diethyl phosphate as an acid source, and the sodium alginate and the dimethylol diethyl phosphate are compounded with a PET matrix material to prepare the adhesive tape for the lithium battery, so that incombustible gas can be generated during the fire disaster of the lithium battery, the concentration of oxygen in the diluted air is reduced, the combustion of the combustible is inhibited, and simultaneously, the phosphorus-containing compound can be converted into phosphoric acid in the combustion process to form acidic substances, so that the surface of the material is dehydrated to form a compact and continuous carbon layer, heat insulation and oxygen isolation can effectively prevent the heat and oxygen transfer, thereby the spread of fire can be slowed down, the influence brought by fire disaster is reduced, the protection effect on surrounding electronic elements is achieved, and the safety of the lithium battery in the use process is improved.
Further, in the step S1, the concentration of the sodium hydroxide is 1-2 mol/L.
Further, in the step S2, the composite catalyst is prepared from 7-8:9-10 of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-lutidine in a mass ratio.
The manufacturing method of the blue insulating tape applied to the lithium battery comprises the following preparation steps:
Placing PET resin, a heat-stable toughening agent, a synergistic flame-retardant compound, a filler, a coupling agent, an antioxidant and pigment in a double-screw extruder, setting the screw rotation speed to be 100-200r/min, and carrying out melt extrusion and calendaring treatment at the temperature of a machine head of 180-200 ℃ to obtain a PET substrate layer;
Coating a release agent solution on one side of the PET substrate layer, transferring the release agent solution into an oven at 80-90 ℃, and taking out the release agent solution after curing for 6-8min to obtain a release layer;
And thirdly, coating an adhesive on the other side of the PET substrate layer, transferring to an oven at 90-100 ℃, solidifying for 30-35min, taking out to obtain an adhesive layer, cooling, cutting and rolling to obtain the blue insulating adhesive tape.
Further, in the second step, the release agent solution is a non-silicon release agent solution.
Further, in the third step, the adhesive is any one of an acrylic adhesive and a silica gel adhesive.
The invention has the beneficial effects that:
According to the invention, the thermal stability and the flame retardant performance of the adhesive tape for the lithium battery are obviously improved by preparing the thermal stability toughening agent and the synergistic flame retardant compound to participate in the preparation process of the PET substrate layer of the adhesive tape for the lithium battery, the influence of a high-temperature environment on the adhesive tape for the lithium battery is weakened, the flame retardant effect can be rapidly exerted when the lithium battery is in a fire disaster, the flame spreading speed is delayed, the flame is extinguished even, the risk caused by the fire disaster spreading is reduced, the protection effect on surrounding electronic elements is also realized, and the service life and the safety of the lithium battery are improved.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of a natural rubber, a heat stable toughening agent according to an embodiment of the present invention;
Fig. 2 is an infrared spectrum of a sodium alginate, modified sodium alginate and synergistic flame retardant composite in an embodiment of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples of the present invention, the preparation methods of the thermally stable tougheners and synergistic flame retardant composites used are as follows:
1. Preparation of thermally stable tougheners
3G of natural rubber is placed in 100ml of toluene, after being fully stirred for 2 hours, 2g of 5-norbornene-2-carboxylic acid is added, 0.02g of azodiisobutyronitrile is added, and the temperature is raised to 60 DEG C
Stirring for 5h, cooling to room temperature, and collecting the product to obtain the heat-stable toughening agent.
Using a Fourier infrared spectrometer to grind and mix the natural rubber and the thermal stabilizing toughening agent with potassium bromide respectively, then tabletting, and carrying out infrared spectrum test, wherein the test spectrum range is 4000-500cm -1, and as can be seen from figure 1, in the infrared spectrum of the natural rubber, the 3056cm -1 part is the absorption peak of the carbon hydrogen bond in alkenyl, and the 2934cm -1 part is the absorption peak of the carbon hydrogen bond in methyl;
In the infrared spectrum of the heat-stable toughening agent, the absorption peak of the ester carbon-oxygen double bond in the carboxyl is shown at 1740cm -1, and compared with the infrared spectrum of the natural rubber, the absorption peak of the hydrocarbon bond in the alkenyl at 3056cm -1 is basically disappeared, which shows that the double bond in the natural rubber structure reacts with the double bond in the 5-norbornene-2-carboxylic acid structure.
2. Preparation of synergistic flame retardant composite
S1, placing 3g of sodium alginate in 100ml of deionized water, fully stirring for 1h, adding 1.2ml of sodium hydroxide with the concentration of 1 mol/L, adjusting the pH to 8, adding 1.5g of 2, 3-pyrazine dianhydride, heating to 55 ℃ for reaction for 3h, and removing the solvent by rotary evaporation to obtain modified sodium alginate;
S2, placing 3g of modified sodium alginate into 120ml of N, N-dimethylformamide, adding 2g of diethyl hydroxymethylphosphonate, 0.07g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.09g of 4-dimethylpyridine, heating to 50 ℃ for reaction for 24 hours, and collecting products after the reaction is completed to obtain the synergistic flame retardant composite.
Grinding and mixing sodium alginate, modified sodium alginate and synergistic flame retardant compound with potassium bromide respectively by using a Fourier infrared spectrometer, tabletting, and carrying out infrared spectrum test, wherein the test spectral range is 4000-500cm -1, as can be seen from FIG. 2, in the infrared spectrum of the sodium alginate, the 3324cm -1 part is an absorption peak of hydroxyl, the 1611cm -1 part is an asymmetric stretching vibration peak of carbon-oxygen double bond in carboxyl, the 1420cm -1 part is a symmetric stretching vibration peak of carbon-oxygen double bond in carboxyl, and the 1102cm -1 part is a stretching vibration peak of carbon-oxygen-carbon single bond in carboxyl; in the infrared spectrum of the modified sodium alginate, compared with the former, the symmetrical stretching vibration peak of the carbon-oxygen double bond in the carboxyl at the position of 1420cm -1 is obviously weakened with the stretching vibration peak of the carbon-oxygen-carbon single bond in the carboxyl at the position of 1102cm -1, and the asymmetrical stretching vibration peak of the carbon-oxygen double bond in the carboxyl at the position of 1611cm -1 is deviated, which is caused by the reaction of the hydroxyl in the sodium alginate structure and 2, 3-pyrazinedioic anhydride; in the infrared spectrum of the synergistic flame-retardant compound, the absorption peak of the phosphorus-oxygen double bond in the phosphate group is at 1256cm -1, the absorption peak of the carbon-oxygen double bond in the ester group is at 1711cm -1, the absorption peak of the phosphorus-oxygen double bond in the phosphate group is at 1256cm -1, and the absorption peak of the carbon-oxygen double bond in the ester group is at 1711cm -1, which are caused by esterification reaction of carboxyl in the modified sodium alginate structure and hydroxyl in the hydroxymethylphosphonate structure.
Example 1
Preparation of PET substrate layer
50 Parts of PET resin, 10 parts of heat-stable toughening agent, 3 parts of synergistic flame retardant compound, 2 parts of nano silicon dioxide, 2 parts of ethyl trimethoxysilane, 3 parts of 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1,3, 5-triazinane-2, 4, 6-trione and 1 part of phthalocyanine blue pigment are placed in a double screw extruder, the rotating speed of the screw is set to be 100r/min, the temperature of a machine head is 180 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Example 2
Preparation of PET substrate layer
70 Parts of PET resin, 12 parts of heat-stable toughening agent, 5 parts of synergistic flame-retardant compound, 4 parts of nano montmorillonite, 3 parts of trimethoxy (propyl) silane and 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid, and 2 parts of cobalt blue pigment are placed in a double screw extruder, the screw rotating speed is set to be 150r/min, the temperature of a machine head is set to be 190 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Example 3
Preparation of PET substrate layer
80 Parts of PET resin, 15 parts of a heat-stable toughening agent, 6 parts of a synergistic flame-retardant composite, 6 parts of halloysite nanotubes, 5 parts of isopropyl trioleate acyloxy titanate, 5 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester and 2 parts of phthalocyanine blue pigment are placed in a double-screw extruder, the screw rotating speed is set to be 200r/min, the temperature of a machine head is set to be 200 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Comparative example 1
Preparation of PET substrate layer
70 Parts of PET resin, 5 parts of synergistic flame-retardant compound, 4 parts of nano montmorillonite, 3 parts of trimethoxy (propyl) silane, 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 2 parts of cobalt blue pigment are placed in a double screw extruder, the rotating speed of the screw is set to be 150r/min, the temperature of a machine head is 190 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Comparative example 2
Preparation of PET substrate layer
70 Parts of PET resin, 12 parts of thermal stabilizing toughening agent, 4 parts of nano montmorillonite, 3 parts of trimethoxy (propyl) silane, 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 2 parts of cobalt blue pigment are placed in a double screw extruder, the screw rotating speed is set to be 150r/min, the temperature of a machine head is 190 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Comparative example 3
Preparation of PET substrate layer
70 Parts of PET resin, 4 parts of nano montmorillonite, 3 parts of trimethoxy (propyl) silane, 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 2 parts of cobalt blue pigment are placed in a double screw extruder, the rotating speed of the screw is set to be 150r/min, the temperature of a machine head is 190 ℃, and the PET substrate layer is obtained through calendaring treatment after melt extrusion.
Comparative example 4
Preparation of PET substrate layer
Placing 70 parts of PET resin, 12 parts of natural rubber, 5 parts of synergistic flame retardant compound, 4 parts of nano montmorillonite, 3 parts of trimethoxy (propyl) silane, 4 parts of 3, 5-di-tert-butyl-4-hydroxybenzoic acid and 2 parts of cobalt blue pigment in a double screw extruder, setting the screw rotating speed to be 150r/min, and carrying out melt extrusion and calendaring treatment at the head temperature of 190 ℃ to obtain a PET substrate layer;
Performance detection
Referring to UL94 flame retardant rating standards, the substrate layers prepared in examples 1 to 3, comparative examples 1 to 4 were prepared into samples conforming to specifications, and vertical combustion tests were performed to determine flame retardant properties of the samples; the substrate layers prepared in examples 1 to 3 and comparative examples 1 to 4 were prepared into 150mm×15mm specimens, and the specimens were subjected to a longitudinal elongation at break test with an XH8650 type universal test stretcher at a test effective length of 100nm and a test speed of 10mm/min; preparing the substrate layers prepared in the examples 1-3 and the comparative examples 1-3 into samples meeting the specification, testing the Vicat softening temperature of the samples with reference to the standard GB/T1633-2000, and judging the thermal stability of the samples; specific detection data are shown in the following table:
As can be seen from the above table, the tapes prepared in examples 1 to 3 have excellent flame retardancy, heat stability and toughness, the tapes prepared in comparative example 1 have excellent flame retardant properties by adding the synergistic flame retardant compound, but the tapes prepared in comparative example 2 have better toughness and heat stability than the tapes prepared in examples, but have poor flame retardant properties by adding the heat stabilizer toughening agent, but have no synergistic flame retardant compound, the tapes prepared in comparative example 3 have neither the heat stabilizer toughening agent nor the synergistic flame retardant compound, and the tapes prepared in comparative example 4 have poor toughness, heat stability by adding the synergistic flame retardant compound, but have excellent flame retardant properties by adding the natural rubber, but have good toughness by not introducing the rigid structure into the natural rubber structure.
Blue insulating tapes were prepared respectively using the PET substrate layers prepared in examples 1 to 3, and the specific production method includes the following steps:
Coating a non-silicon release agent solution on one side of a PET substrate layer, transferring to an oven at 85 ℃, and taking out the PET substrate layer before curing for 7min to obtain a release layer;
Coating a silica gel adhesive on the other side of the PET substrate layer, transferring to a 95 ℃ oven, solidifying for 32min, taking out to obtain an adhesive layer, cooling, cutting, and rolling to obtain the blue insulating adhesive tape.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar alternatives may be made by those skilled in the art, without departing from the scope of the invention as defined by the principles of the invention.

Claims (10)

1. The blue insulating tape applied to the lithium battery is characterized by comprising a substrate layer, a release layer and an adhesive layer; the release layer and the adhesive layer are distributed on two sides of the substrate layer; the substrate layer comprises the following raw materials in parts by weight: 50-80 parts of PET resin, 2-6 parts of filler, 2-5 parts of coupling agent, 3-5 parts of antioxidant and 1-3 parts of pigment; the substrate layer also comprises 10-15 parts of heat-stable toughening agent and 3-6 parts of synergistic flame-retardant compound; the thermal stabilizing toughening agent is prepared by reacting natural rubber with 5-norbornene-2-carboxylic acid; the synergistic flame-retardant compound is prepared by sequentially reacting sodium alginate with 2, 3-pyrazinedicarboxylic anhydride and diethyl hydroxymethylphosphonate.
2. The blue insulating tape for lithium battery according to claim 1, wherein the filler is any one of nano silicon dioxide, nano montmorillonite, halloysite nanotube and nano kieselguhr; the coupling agent is any one of a silane coupling agent and a titanate coupling agent; the antioxidant is a hindered phenol antioxidant; the pigment is any one of phthalocyanine blue pigment and cobalt blue pigment.
3. The blue insulating tape for lithium batteries according to claim 1, wherein the preparation method of the heat-stable toughening agent is as follows:
And (3) placing the natural rubber in toluene, fully stirring for 2-3 hours, adding 5-norbornene-2-carboxylic acid, adding an initiator, heating to 60-70 ℃, stirring for 5-8 hours, cooling to room temperature, and collecting a product to obtain the heat-stable toughening agent.
4. The blue insulating tape for lithium battery according to claim 3, wherein the initiator is any one of azobisisobutyronitrile and azobisisoheptonitrile.
5. The blue insulating tape for lithium batteries according to claim 1, wherein the preparation method of the synergistic flame retardant composite is as follows:
S1, placing sodium alginate in deionized water, fully stirring for 1-2 hours, adding sodium hydroxide, adjusting the pH to 8-9, adding 2, 3-pyrazinedianhydride, heating to 55-65 ℃ for reaction for 3-5 hours, and removing the solvent by rotary evaporation to obtain modified sodium alginate;
S2, placing the modified sodium alginate in N, N-dimethylformamide, adding the diethyl hydroxymethylphosphonate and the composite catalyst, heating to 50-60 ℃ for reaction for 24-48h, and collecting the product after the reaction is completed to obtain the synergistic flame-retardant compound.
6. The blue insulating tape for lithium battery according to claim 5, wherein in the step S1, the concentration of sodium hydroxide is 1-2mol/L.
7. The blue insulating tape for lithium battery according to claim 5, wherein in the step S2, the composite catalyst is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 4-dimethylpyridine in a mass ratio of 7-8:9-10.
8. A method for manufacturing the blue insulating tape for lithium batteries according to claim 1, comprising the steps of:
Placing PET resin, a heat-stable toughening agent, a synergistic flame-retardant compound, a filler, a coupling agent, an antioxidant and pigment in a double-screw extruder, setting the screw rotation speed to be 100-200r/min, and carrying out melt extrusion and calendaring treatment at the temperature of a machine head of 180-200 ℃ to obtain a PET substrate layer;
Coating a release agent solution on one side of the PET substrate layer, transferring the release agent solution into an oven at 80-90 ℃, and taking out the release agent solution after curing for 6-8min to obtain a release layer;
And thirdly, coating an adhesive on the other side of the PET substrate layer, transferring to an oven at 90-100 ℃, solidifying for 30-35min, taking out to obtain an adhesive layer, cooling, cutting and rolling to obtain the blue insulating adhesive tape.
9. The method of claim 8, wherein in the second step, the mold release solution is a non-silicon mold release solution.
10. The method for manufacturing a blue insulating tape for a lithium battery according to claim 8, wherein in the third step, the adhesive is any one of an acrylic adhesive and a silicone adhesive.
CN202410007574.5A 2024-01-03 2024-01-03 Blue insulating tape applied to lithium battery and manufacturing method thereof Active CN117903711B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674947A (en) * 1994-08-16 1997-10-07 Mitsui Toatsu Chemicals, Inc. Method for preparing modified resins and their applications
US20070207186A1 (en) * 2006-03-04 2007-09-06 Scanlon John J Tear and abrasion resistant expanded material and reinforcement
US20110067799A1 (en) * 2008-04-30 2011-03-24 Tesa Se Adhesive tape
WO2017197551A1 (en) * 2016-05-16 2017-11-23 东莞市澳中电子材料有限公司 Adhesive tape for improving anti-dropping capacity of battery and manufacturing method therefor
WO2021243836A1 (en) * 2020-06-03 2021-12-09 山东科技大学 Flame-retardant masterbatch, preparation method therefor, and application thereof
CN117165214A (en) * 2023-09-26 2023-12-05 江西昊泽光学膜科技有限公司 High-temperature-resistant composite adhesive tape and production process thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674947A (en) * 1994-08-16 1997-10-07 Mitsui Toatsu Chemicals, Inc. Method for preparing modified resins and their applications
US20070207186A1 (en) * 2006-03-04 2007-09-06 Scanlon John J Tear and abrasion resistant expanded material and reinforcement
US20110067799A1 (en) * 2008-04-30 2011-03-24 Tesa Se Adhesive tape
WO2017197551A1 (en) * 2016-05-16 2017-11-23 东莞市澳中电子材料有限公司 Adhesive tape for improving anti-dropping capacity of battery and manufacturing method therefor
WO2021243836A1 (en) * 2020-06-03 2021-12-09 山东科技大学 Flame-retardant masterbatch, preparation method therefor, and application thereof
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