CN115572548A - High-shear-strength insulating hot melt adhesive film for metal-shell power battery and preparation method thereof - Google Patents
High-shear-strength insulating hot melt adhesive film for metal-shell power battery and preparation method thereof Download PDFInfo
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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
- C09J7/10—Adhesives in the form of films or foils without carriers
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
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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
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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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
- 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
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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
Abstract
The invention relates to the technical field of hot melt adhesive film materials, and particularly discloses a high-shear-strength insulating hot melt adhesive film for a metal-shell power battery, which comprises the following raw materials in parts by weight: 30-40 parts of polyester resin, 10-15 parts of polyolefin resin, 8-12 parts of tackifying resin, 5-10 parts of rare earth compound coupling agent modified hydroxyapatite, 3-6 parts of modified boron nitride, 3-6 parts of hydroxyl silicone oil, 2-5 parts of cross-linking agent and 45-55 parts of acetone. The hot melt adhesive film adopts polyester resin and polyolefin resin, increases the compatibility between the raw materials of the product by adding tackifying resin and hydroxyl silicone oil as auxiliary agents, improves the insulativity and the shear strength of the product by using rare earth compound coupling agent to modify hydroxyapatite and modified boron nitride, and performing synergistic coordination and synergistic coordination between the hydroxyapatite and the modified boron nitride, and improves the performance of the product by obtaining a coordinated enhancement effect, and the raw materials are mutually coordinated and mutually promoted to improve the performance effect of the product.
Description
Technical Field
The invention relates to the technical field of hot melt adhesive films, in particular to a high-shear-strength insulating hot melt adhesive film for a metal-shell power battery and a preparation method thereof.
Background
The hot melt adhesive film is a film product with or without release paper, and can be operated continuously or intermittently conveniently. Can be widely used for bonding various fabrics, paper, high polymer materials and metals. Can be bonded with various materials such as metal, plastic, paper, wood, ceramics, textile fabrics and the like, and can also obtain good effect when being bonded on the surface of an uneven object; the adhesive is mainly used for bonding nameplates, plastics and hardware, bonding and fixing metal shells of electronic products, bonding and fixing reinforcing plates, laminating and bonding smart cards and chip passports, bonding window frames and front covers of mobile phones, bonding battery tanks of cameras and the like.
The invention provides a high-shear-strength insulating hot-melt adhesive film for a metal-shell power battery and a preparation method thereof based on the technical point that the insulating property and the shear strength of the existing hot-melt adhesive film for the power battery cannot be coordinately improved, and the insulating property and the shear strength are coordinately improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-shear-strength insulating hot melt adhesive film for a metal-shell power battery and a preparation method thereof, so as to solve the problems in the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a high-shear-strength insulating hot melt adhesive film for a metal-shell power battery, which comprises the following raw materials in parts by weight:
30-40 parts of polyester resin, 10-15 parts of polyolefin resin, 8-12 parts of tackifying resin, 5-10 parts of rare earth compound coupling agent modified hydroxyapatite, 3-6 parts of modified boron nitride, 3-6 parts of hydroxyl silicone oil, 2-5 parts of cross-linking agent and 45-55 parts of acetone.
Preferably, the hot melt adhesive film comprises the following raw materials in parts by weight:
35 parts of polyester resin, 12.5 parts of polyolefin resin, 10 parts of tackifying resin, 7.5 parts of rare earth compound coupling agent modified hydroxyapatite, 4.5 parts of modified boron nitride, 4.5 parts of hydroxyl silicone oil, 3.5 parts of cross-linking agent and 50 parts of acetone.
Preferably, the tackifying resin is a C5 petroleum resin; the crosslinking agent is diethylenetriamine.
Preferably, the preparation method of the rare earth compound coupling agent modified hydroxyapatite comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to the weight ratio of 1;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 5-10% according to the weight ratio of 1;
s03: adding the pre-modified hydroxyapatite into 3-5 times of the S01 product, stirring for reaction, washing with water, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
Preferably, the mass fraction of the sodium alginate solution is 10-20%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
Preferably, the stirring reaction temperature is 55-65 ℃, the stirring time is 30-40min, and the stirring speed is 350-450r/min.
Preferably, the preparation method of the modified boron nitride comprises the following steps:
s11: adding 30-40 parts of boron nitride into 50-60 parts of ethanol, uniformly dispersing, then adding 2-5 parts of hydrochloric acid and 1-3 parts of sodium oxalate, and fully stirring and mixing;
s12: adding 3-6 parts of diatomite and 1-5 parts of tween 60 into 5-10 parts of chitosan aqueous solution, uniformly stirring, then adding 1-3 parts of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an additive modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
Preferably, the mass fraction of the chitosan aqueous solution is 10-15%.
The invention also provides a preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-shell power battery, which comprises the following steps of:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-ingredient;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to a hot pressing machine at the temperature of 75-85 ℃ for 10-20min, wherein the hot pressing pressure is 10-20MPa, and finishing the hot pressing to obtain the hot melt adhesive film.
Preferably, the rotation speed of the primary mixing is 550-650r/min, and the mixing time is 10-20min; the rotation speed of the secondary mixing is 1000-1200r/min, and the mixing time is 20-30min.
Compared with the prior art, the invention has the following beneficial effects:
the hot melt adhesive film adopts polyester resin and polyolefin resin, increases the compatibility between the raw materials of the product by adding tackifying resin and hydroxyl silicone oil as auxiliary agents, improves the insulativity and the shear strength of the product by using rare earth compound coupling agent to modify hydroxyapatite and modified boron nitride, and performing synergistic coordination and synergistic coordination between the hydroxyapatite and the modified boron nitride, and improves the performance of the product by obtaining a coordinated enhancement effect, and the raw materials are mutually coordinated and mutually promoted to improve the performance effect of the product.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following raw materials in parts by weight:
30-40 parts of polyester resin, 10-15 parts of polyolefin resin, 8-12 parts of tackifying resin, 5-10 parts of rare earth compound coupling agent modified hydroxyapatite, 3-6 parts of modified boron nitride, 3-6 parts of hydroxyl silicone oil, 2-5 parts of cross-linking agent and 45-55 parts of acetone.
The hot melt adhesive film of the embodiment comprises the following raw materials in parts by weight:
35 parts of polyester resin, 12.5 parts of polyolefin resin, 10 parts of tackifying resin, 7.5 parts of rare earth compound coupling agent modified hydroxyapatite, 4.5 parts of modified boron nitride, 4.5 parts of hydroxyl silicone oil, 3.5 parts of cross-linking agent and 50 parts of acetone.
The tackifying resin of this example is a C5 petroleum resin; the crosslinking agent is diethylenetriamine.
The preparation method of the rare earth compound coupling agent modified hydroxyapatite comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to a weight ratio of 1:5, then adding a coupling agent KH560 accounting for 10-20% of the total weight of the rare earth lanthanum sulfate and a phosphoric acid buffer solution accounting for 1-5% of the total weight of the rare earth lanthanum sulfate, and uniformly stirring;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 5-10% according to the weight ratio of 1;
s03: adding the pre-modified hydroxyapatite into 3-5 times of the S01 product, stirring for reaction, washing with water, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
The mass fraction of the sodium alginate solution in the embodiment is 10-20%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
The stirring reaction temperature of the embodiment is 55-65 ℃, the stirring time is 30-40min, and the stirring speed is 350-450r/min.
The preparation method of the modified boron nitride of the embodiment comprises the following steps:
s11: adding 30-40 parts of boron nitride into 50-60 parts of ethanol, uniformly dispersing, then adding 2-5 parts of hydrochloric acid and 1-3 parts of sodium oxalate, and fully stirring and mixing;
s12: adding 3-6 parts of diatomite and 1-5 parts of tween 60 into 5-10 parts of chitosan aqueous solution, uniformly stirring, then adding 1-3 parts of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an additive modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
The mass fraction of the chitosan aqueous solution in this example was 10-15%.
The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following steps:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-prepared material;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to a hot pressing machine at the temperature of 75-85 ℃ for 10-20min, wherein the hot pressing pressure is 10-20MPa, and finishing the hot pressing to obtain the hot melt adhesive film.
The rotation speed of the primary mixing is 550-650r/min, and the mixing time is 10-20min; the rotation speed of the secondary mixing is 1000-1200r/min, and the mixing time is 20-30min.
Example 1.
The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following raw materials in parts by weight:
30 parts of polyester resin, 10 parts of polyolefin resin, 8 parts of tackifying resin, 5 parts of rare earth compound coupling agent modified hydroxyapatite, 3 parts of modified boron nitride, 3 parts of hydroxyl silicone oil, 2 parts of cross-linking agent and 45 parts of acetone.
The tackifying resin of this example is a C5 petroleum resin; the crosslinker is diethylenetriamine.
The preparation method of the rare earth compound coupling agent modified hydroxyapatite of the embodiment comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to a weight ratio of 1;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 5% according to the weight ratio of 1;
s03: and adding the pre-modified hydroxyapatite into 3 times of the S01 product, stirring for reaction, washing with water after stirring is finished, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
The mass fraction of the sodium alginate solution in this example is 10%; the pH value of the phosphoric acid buffer solution is 4.5.
In the present example, the temperature of the stirring reaction was 55 ℃, the stirring time was 30min, and the stirring speed was 350r/min.
The preparation method of the modified boron nitride of the embodiment comprises the following steps:
s11: adding 30 parts of boron nitride into 50 parts of ethanol, uniformly dispersing, then adding 2 parts of hydrochloric acid and 1 part of sodium oxalate, and stirring and fully mixing;
s12: adding 3 parts of diatomite and 1 part of tween 60 into 5 parts of chitosan aqueous solution, uniformly stirring, then adding 1 part of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an additive modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
The mass fraction of the chitosan aqueous solution in this example was 10%.
The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following steps:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-prepared material;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to a hot pressing machine at 75 ℃ for 10min, wherein the hot pressing pressure is 10MPa, and finishing the hot pressing to obtain the hot-melt adhesive film.
The rotation speed of the primary mixing of the embodiment is 550r/min, and the mixing time is 10min; the rotation speed of the secondary mixing is 1000r/min, and the mixing time is 20min.
Example 2.
The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following raw materials in parts by weight:
40 parts of polyester resin, 15 parts of polyolefin resin, 12 parts of tackifying resin, 10 parts of rare earth compound coupling agent modified hydroxyapatite, 6 parts of modified boron nitride, 6 parts of hydroxyl silicone oil, 5 parts of cross-linking agent and 55 parts of acetone.
The tackifying resin of this example is a C5 petroleum resin; the crosslinking agent is diethylenetriamine.
The preparation method of the rare earth compound coupling agent modified hydroxyapatite of the embodiment comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to the weight ratio of 1;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 10% according to the weight ratio of 1;
s03: and adding the pre-modified hydroxyapatite into 5 times of the S01 product, stirring for reaction, washing with water after stirring, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
The mass fraction of the sodium alginate solution in this example is 20%; the pH value of the phosphoric acid buffer solution is 5.5.
In the present example, the stirring reaction temperature was 65 ℃, the stirring time was 40min, and the stirring speed was 450r/min.
The preparation method of the modified boron nitride of the embodiment comprises the following steps:
s11: adding 40 parts of boron nitride into 60 parts of ethanol, uniformly dispersing, adding 5 parts of hydrochloric acid and 3 parts of sodium oxalate, and stirring and fully mixing;
s12: adding 6 parts of diatomite and 5 parts of tween 60 into 10 parts of chitosan aqueous solution, uniformly stirring, then adding 3 parts of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an addition modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
The mass fraction of the chitosan aqueous solution in this example was 15%.
The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-case power battery comprises the following steps:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-ingredient;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to 85 ℃ for hot pressing for 20min, wherein the hot pressing pressure is 20MPa, and finishing the hot pressing to obtain the hot-melt adhesive film.
The rotation speed of the primary mixing of the embodiment is 650r/min, and the mixing time is 20min; the rotation speed of the secondary mixing is 1200r/min, and the mixing time is 30min.
Example 3.
The high-shear-strength insulating hot melt adhesive film for the metal-case power battery comprises the following raw materials in parts by weight:
35 parts of polyester resin, 12.5 parts of polyolefin resin, 10 parts of tackifying resin, 7.5 parts of rare earth compound coupling agent modified hydroxyapatite, 4.5 parts of modified boron nitride, 4.5 parts of hydroxyl silicone oil, 3.5 parts of cross-linking agent and 50 parts of acetone.
The tackifying resin of this example is a C5 petroleum resin; the crosslinking agent is diethylenetriamine.
The preparation method of the rare earth compound coupling agent modified hydroxyapatite comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to the weight ratio of 1;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 7.5% according to the weight ratio of 1;
s03: and adding the pre-modified hydroxyapatite into 4 times of the S01 product, stirring for reaction, washing with water after stirring, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
The mass fraction of the sodium alginate solution in this example is 15%; the pH value of the phosphoric acid buffer solution is 5.0.
In the present example, the stirring reaction temperature was 60 ℃, the stirring time was 35min, and the stirring speed was 400r/min.
The preparation method of the modified boron nitride of the embodiment comprises the following steps:
s11: adding 45 parts of boron nitride into 55 parts of ethanol, uniformly dispersing, then adding 3.5 parts of hydrochloric acid and 2 parts of sodium oxalate, and stirring and mixing fully;
s12: adding 4.5 parts of diatomite and 3 parts of tween 60 into 7.5 parts of chitosan aqueous solution, uniformly stirring, then adding 2 parts of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an addition modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
The mass fraction of the chitosan aqueous solution in this example was 12.5%.
The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-shell power battery comprises the following steps:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-ingredient;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to 80 ℃ for hot pressing for 15min, wherein the hot pressing pressure is 15MPa, and finishing the hot pressing to obtain the hot-melt adhesive film.
The rotation speed of the primary mixing in the embodiment is 600r/min, and the mixing time is 15min; the rotation speed of the secondary mixing is 1100r/min, and the mixing time is 25min.
Comparative example 1.
Different from the embodiment 3, the method is to add no rare earth compound coupling agent to modify the hydroxyapatite.
Comparative example 2.
Different from the embodiment 3, the rare earth compound coupling agent modified hydroxyapatite is replaced by hydroxyapatite.
Comparative example 3.
Different from the embodiment 3, the preparation method of the hydroxyapatite modified by the rare earth compound coupling agent has no pre-modified treatment on the hydroxyapatite.
Comparative example 4.
Different from the embodiment 3, the preparation of the rare earth compound coupling agent modified hydroxyapatite does not add rare earth lanthanum sulfate.
Comparative example 5.
Unlike example 3, no modified boron nitride was added.
Comparative example 6.
The difference from the example 3 is that no modifier is added in the preparation of the modified boron nitride.
Comparative example 7.
The difference from example 3 is that modified boron nitride is replaced by boron nitride.
The results of the performance measurements of examples 1 to 3 and comparative examples 1 to 7 are as follows
From examples 1 to 3 and comparative examples 1 to 7,
the product of example 3 has excellent puncture resistance and high shear strength, and at the same time, the product resists cycles of high and low temperatures ranging from-40 ℃ to 85 ℃, the performance is still stable, and the product has excellent puncture resistance;
the rare earth compound coupling agent is adopted to modify hydroxyapatite and modified boron nitride, and the two have synergistic effect, so that the puncture resistance and the shear strength of the product are enhanced;
as can be seen from comparative examples 1-4, the shear strength of the product is remarkably reduced without adding the rare earth compound coupling agent modified hydroxyapatite, and meanwhile, the breakdown resistance performance is deteriorated under the conventional conditions, and particularly, the breakdown performance is remarkably reduced under the high and low temperature resistant circulation of-40 to 85 ℃;
in addition, the performance effect of the product is not obviously improved by replacing the rare earth compound coupling agent with the hydroxyapatite, and the performance effect of the product is different due to different preparation methods of replacing the rare earth compound coupling agent with the hydroxyapatite;
it can be seen from comparative examples 5-7 that modified boron nitride is not added, and is replaced by boron nitride, and meanwhile, no modifier is added during the preparation of boron nitride, the performance effect of the product tends to be worsened, only the modified boron nitride prepared by the method of the invention and the rare earth compound coupling agent modified hydroxyapatite of the invention are used in coordination, the insulation, breakdown resistance and shear strength performance effects of the product are enhanced in a coordinated manner, and meanwhile, the performance stability of the product is still excellent in an acid environment.
The invention carries out further optimization treatment on the aging of the product at the temperature of 50 ℃ within 2000 hours:
the aging resistance experiment shows that the product still has stable performance after aging resistance, the stability of the product of the comparative example is obviously poor, and the performance stability of the product is obvious by adopting the raw material proportion of the invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery is characterized by comprising the following raw materials in parts by weight:
30-40 parts of polyester resin, 10-15 parts of polyolefin resin, 8-12 parts of tackifying resin, 5-10 parts of rare earth compound coupling agent modified hydroxyapatite, 3-6 parts of modified boron nitride, 3-6 parts of hydroxyl silicone oil, 2-5 parts of cross-linking agent and 45-55 parts of acetone.
2. The high-shear-strength insulating hot melt adhesive film for the metal-shelled power battery as claimed in claim 1, wherein the hot melt adhesive film comprises the following raw materials in parts by weight:
35 parts of polyester resin, 12.5 parts of polyolefin resin, 10 parts of tackifying resin, 7.5 parts of rare earth compound coupling agent modified hydroxyapatite, 4.5 parts of modified boron nitride, 4.5 parts of hydroxyl silicone oil, 3.5 parts of cross-linking agent and 50 parts of acetone.
3. The high-shear-strength insulating hot melt adhesive film for the metal-cased power battery as claimed in claim 1, wherein the tackifying resin is a C5 petroleum resin; the crosslinking agent is diethylenetriamine.
4. The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery according to claim 1, wherein the preparation method of the rare earth compound coupling agent modified hydroxyapatite comprises the following steps:
s01: adding rare earth lanthanum sulfate into a sodium alginate solution according to a weight ratio of 1:5, then adding a coupling agent KH560 accounting for 10-20% of the total weight of the rare earth lanthanum sulfate and a phosphoric acid buffer solution accounting for 1-5% of the total weight of the rare earth lanthanum sulfate, and uniformly stirring;
s02: adding hydroxyapatite into a hydrochloric acid solution with the mass fraction of 5-10% according to the weight ratio of 1;
s03: adding the pre-modified hydroxyapatite into 3-5 times of the S01 product, stirring for reaction, washing with water, and drying to obtain the rare earth compound coupling agent modified hydroxyapatite.
5. The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery as claimed in claim 4, wherein the mass fraction of the sodium alginate solution is 10-20%; the pH value of the phosphoric acid buffer solution is 4.5-5.5.
6. The high-shear-strength insulating hot melt adhesive film for the metal-shelled power battery as claimed in claim 4, wherein the stirring reaction temperature is 55-65 ℃, the stirring time is 30-40min, and the stirring rotation speed is 350-450r/min.
7. The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery as claimed in claim 1, wherein the preparation method of the modified boron nitride comprises the following steps:
s11: adding 30-40 parts of boron nitride into 50-60 parts of ethanol, uniformly dispersing, then adding 2-5 parts of hydrochloric acid and 1-3 parts of sodium oxalate, and fully stirring and mixing;
s12: adding 3-6 parts of diatomite and 1-5 parts of tween 60 into 5-10 parts of chitosan aqueous solution, uniformly stirring, then adding 1-3 parts of sodium dimercaptopropane sulfonate, and fully stirring and mixing to obtain an additive modifier;
s13: and adding the modifier into the product S11 according to the weight ratio of 1.
8. The high-shear-strength insulating hot melt adhesive film for the metal-shell power battery as claimed in claim 7, wherein the mass fraction of the chitosan aqueous solution is 10-15%.
9. The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-shell power battery as defined in any one of claims 1 to 8, wherein the method comprises the following steps:
firstly, fully mixing polyester resin, polyolefin resin, tackifying resin, hydroxy silicone oil and acetone at one time to obtain a pre-ingredient;
secondly, adding a rare earth compound coupling agent modified hydroxyapatite, modified boron nitride and a cross-linking agent, and fully mixing for the second time to obtain a glue film material;
and step three, feeding the adhesive film material to a hot pressing machine at the temperature of 75-85 ℃ for 10-20min, wherein the hot pressing pressure is 10-20MPa, and finishing the hot pressing to obtain the hot melt adhesive film.
10. The preparation method of the high-shear-strength insulating hot melt adhesive film for the metal-case power battery as claimed in claim 9, wherein the rotation speed of the primary mixing is 550-650r/min, and the mixing time is 10-20min; the rotation speed of the secondary mixing is 1000-1200r/min, and the mixing time is 20-30min.
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| CN115975374A (en) * | 2023-02-20 | 2023-04-18 | 广东顾纳凯材料科技有限公司 | Flame-retardant polyolefin composite material and preparation method thereof |
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