CN113604159B - Degradable swelling adhesive tape for lithium ion battery and preparation method thereof - Google Patents

Degradable swelling adhesive tape for lithium ion battery and preparation method thereof Download PDF

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Publication number
CN113604159B
CN113604159B CN202111074383.3A CN202111074383A CN113604159B CN 113604159 B CN113604159 B CN 113604159B CN 202111074383 A CN202111074383 A CN 202111074383A CN 113604159 B CN113604159 B CN 113604159B
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parts
curing agent
degradable
lithium ion
swelling
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CN113604159A (en
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万中梁
梁龙
李奎
李俊生
方超超
夏金明
芮鹏程
宋世杰
张东星
乐海霞
朱润雨
李鑫
刘杰
刘伟
汪峰
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Wuhu Huishi New Material Technology Co ltd
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Wuhu Huishi 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
    • 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
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a degradable swelling adhesive tape for a lithium ion battery and a preparation method thereof, wherein the degradable swelling adhesive tape for the lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight: 30-50 parts of polytrimethylene carbonate; 30-50 parts of polybutylene succinate; 2-8 parts of a curing agent; 0-1.5 parts of a catalyst; 100 portions and 120 portions of solvent; the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight: 8-12 parts of polybutylene succinate; 0.3-0.8 part of curing agent; 0-0.05 part of catalyst; 45-55 parts of a solvent; the matrix resin in the basal layer and the matrix resin in the adhesive layer of the swelling adhesive tape for the degradable lithium ion battery provided by the invention are both made of degradable materials, so that the adhesive tape can be degraded under the condition of swelling in electrolyte, the environmental pollution is reduced to a great extent, and the environmental protection requirement is met.

Description

Degradable swelling adhesive tape for lithium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of swelling adhesive tapes, and particularly relates to a degradable swelling adhesive tape for a lithium ion battery and a preparation method thereof.
Background
When the cylindrical battery is assembled, a certain gap exists between the battery core and the cylindrical shell, if the battery core cannot be effectively fixed in the shell, the battery core can move in the shell after vibration or external impact occurs, so that the internal resistance of the battery can be increased or electrode plates can be damaged, and the performance of the battery can be greatly degraded. Therefore, during assembly, the gap must be filled and effective adhesion between the cell and the cylindrical shell is achieved, and the use of the swelling tape is an effective means for achieving the purpose.
However, most of the swelling tapes have a base layer prepared from PVAC, SBS or the like as a base resin, and although the swelling tape has a good swelling effect, the swelling tape is undegradable and does not satisfy environmental requirements.
Disclosure of Invention
In order to solve the technical problems, the invention provides a degradable swelling adhesive tape for a lithium ion battery and a preparation method thereof, wherein the degradable swelling adhesive tape has degradability and a swelling effect, and the swelling rate can reach more than 200%.
The technical scheme adopted by the invention is as follows:
the swelling adhesive tape for the degradable lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000011
Figure BDA0003261699870000021
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000022
further, the polytrimethylene carbonate in the substrate layer is replaced by any one or two of polylactic acid and polycaprolactone; or, the polytrimethylene carbonate in the substrate layer is replaced with a combination of polytrimethylene carbonate and any two or three of polylactic acid and polycaprolactone.
The molecular weights of the polytrimethylene carbonate, the polylactic acid, the polycaprolactone and the polybutylene succinate are all 6-20 ten thousand, and if the molecular weights are too high, the polytrimethylene carbonate, the polycaprolactone and the polybutylene succinate cannot be dissolved in a solvent, and the volume swelling effect of the adhesive tape in an electrolyte cannot be ensured; if the molecular weight is too low, even by curing and crosslinking, the resulting adhesive tape is easily dissolved by the electrolyte, and the swelling effect cannot be satisfied.
The curing agent is an isocyanate curing agent or an amino resin curing agent, and the curing agent can realize the curing and crosslinking of polytrimethylene carbonate and polybutylene succinate.
When the curing agent is an isocyanate curing agent, the dosage of the catalyst is 0, namely, only the isocyanate curing agent with a specific dosage is used as the curing agent, so that the curing crosslinking of any one or more of polytrimethylene carbonate, polylactic acid and polycaprolactone in the substrate layer and the polybutylene succinate can be realized; the curing and crosslinking of the poly butylene succinate in the pressure-sensitive adhesive layer can be realized.
When the curing agent is an amino resin curing agent, the catalyst is p-toluenesulfonic acid; in the base layer, the mass ratio of the amino resin curing agent to the p-toluenesulfonic acid is 2-8: 1; in the pressure-sensitive adhesive layer, the mass ratio of the amino resin curing agent to the p-toluenesulfonic acid is 45-55: 1. When the amino resin curing agent is used as the curing agent, one or more of polytrimethylene carbonate, polylactic acid and polycaprolactone in the substrate layer and the polybutylene succinate can be cured and crosslinked by matching with p-toluenesulfonic acid as a catalyst; the curing and crosslinking of the poly (butylene succinate) in the pressure-sensitive adhesive layer can be realized.
The solvent is N, N-dimethylformamide or ethyl acetate.
The thickness of the substrate layer is 30-50 μm, and the thickness of the pressure-sensitive adhesive layer is 3-10 μm, so that a customer can conveniently and automatically load the pressure-sensitive adhesive layer into a steel shell of a cylindrical battery when using the cylindrical battery; if the thickness of the base layer is too thin, the hardness of the adhesive tape is low, the adhesive tape is easy to wrinkle when a client uses the adhesive tape on a machine, and the phenomenon of poor adhesive tape pasting occurs; if the thickness of the pressure-sensitive adhesive layer is relatively thin, the adhesiveness of the adhesive tape is too low to stick to the cell.
The invention also provides a preparation method of the swelling adhesive tape for the degradable lithium ion battery, which comprises the following steps:
(1) dissolving polytrimethylene carbonate, polylactic acid, polycaprolactone and polybutylene succinate in a solvent according to a formula ratio;
(2) diluting a curing agent and a catalyst in a formula amount by using a solvent, adding the diluted curing agent and the catalyst into the step (1), uniformly stirring, and filtering a base solution;
(3) coating the substrate liquid on the release surface of the PET single-sided silicon release film, curing and drying to obtain a substrate layer, and carrying out corona treatment on the substrate layer;
(4) dissolving the polybutylene succinate with the formula amount by using a solvent;
(5) diluting the curing agent and the catalyst according to the formula amount by using a solvent, adding the diluted curing agent and the catalyst into the step (4), uniformly stirring, and filtering to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film, and curing and drying to obtain a pressure-sensitive adhesive layer;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
The thickness of the PET single-sided silicon release film is 15-30 mu m; the release film with the thickness ensures that the basal layer and the glue layer can not shrink and be coiled in the drying and curing process.
The dyne value of the base layer after corona treatment is greater than or equal to 52 dyne.
In the step (2), the stirring temperature is 20-40 ℃, the stirring speed is 600-800 rpm, and the stirring time is 2-3h, under such conditions, the obtained substrate liquid has proper viscosity and is convenient to coat.
In the step (2) and the step (5), a 400-plus 500-mesh double-layer filter screen is used for filtering.
In the step (5), the stirring is performed at 600 revolutions per minute of 400-60 min.
In the step (3), the coating speed is 8-12m/min, and the coating enters an oven for curing and drying at the speed, wherein the oven has 8 sections, and the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃. If the coating speed is too slow, the efficiency is too low, which may result in excessive crosslinking of the resin in the substrate layer and poor swelling effect; if the solvent cannot be uniformly dried at too high coating speed, a large number of small bubbles are easily generated on the substrate layer to influence the appearance, the crosslinking degree is not enough, the dissolving risk is easily generated, and the service life of the adhesive tape is shortened; the drying is carried out by adopting the temperatures of two ends which are low and the middle which is high, so that the solvent can be uniformly dried, the occurrence of bubbles on the basal layer is reduced, and the drying is ensured.
In the step (6), the coating speed is 25-35m/min, and the coating enters an oven for curing and drying at the speed, wherein the oven has 8 sections, and the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃. Too slow a coating speed to be efficient; if the coating speed is too fast, the solvent cannot be uniformly dried, and degumming is easy to occur; when drying, the temperature of the two ends is low and the temperature of the middle is high, so that the solvent can be uniformly dried, and the full crosslinking of the viscose layer is ensured.
According to the swelling adhesive tape for the degradable lithium ion battery, provided by the invention, the basal layer raw material and the pressure-sensitive adhesive layer raw material are selected, so that the adhesive tape can be ensured to have degradability under the condition of effective swelling in electrolyte, and can be used for filling a gap between a battery core and a cylindrical shell of a cylindrical battery after swelling, so that the battery core and the cylindrical shell of the cylindrical battery can be effectively fixed, and the damage to the battery caused by vibration or impact is avoided.
According to the preparation method of the swelling adhesive tape for the degradable lithium ion battery, the substrate layer and the pressure-sensitive adhesive layer are uniformly coated by controlling the substrate liquid mixing condition, the pressure-sensitive adhesive liquid mixing condition and the coating speed; the temperature of each section of the oven is controlled to further control the crosslinking speed of the base layer raw material and the sufficient crosslinking of the pressure-sensitive adhesive layer raw material, so that the preparation of the swelling adhesive tape for the degradable lithium ion battery is realized.
Compared with the prior art, the substrate layer and the adhesive layer of the swelling adhesive tape for the degradable lithium ion battery provided by the invention are made of degradable materials, such as polytrimethylene carbonate (PTMC) in the substrate layer, polylactic acid (PLA), polycaprolactone, polybutylene succinate (PBS) in the substrate layer and the pressure-sensitive adhesive layer, the hardness of the swelling adhesive tape for the degradable lithium ion battery prepared by the method is proper, so that the swelling adhesive tape is convenient for the on-machine operation of a host machine factory, and the swelling adhesive tape can keep a better swelling rate, is degradable, reduces environmental pollution to a great extent, and meets the requirement of environmental protection; the composite material can realize thickness swelling in different degrees in electrolytes with different temperatures, the swelling value in the electrolyte at 45-50 ℃ can reach 195-280%, the swelling value in the electrolyte at 60 ℃ can reach 240-300%, and the swelling value in the electrolyte at 85 ℃ can reach 205-315%.
The swelling adhesive tape for the degradable lithium ion battery provided by the invention can swell in the following solvents, such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, propylene carbonate, ethylene carbonate and propylene carbonate.
Detailed Description
The present invention will be described in detail with reference to examples.
The thickness of the PET single-sided silicon release film used in each of the examples and comparative examples was 25 μm.
PTMC and PBS of the same manufacturer and batch are used in each example and comparative example.
The isocyanate curing agent used in each of the examples and comparative examples was sold under the brand name 3C85 manufactured by Athou Add adhesive products, Inc.
The amino resin curing agent used in each example and comparative example was 582-2, a wood resin.
Example 1
The swelling adhesive tape for the degradable lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000061
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
10 parts of polybutylene succinate;
0.5 part of isocyanate curing agent;
and 50 parts of DMF.
The preparation method of the swelling adhesive tape for the degradable lithium ion battery comprises the following steps:
(1) dissolving polytrimethylene carbonate and polybutylene succinate in a formula amount of 100 parts of DMF;
(2) diluting the isocyanate curing agent with the formula amount by 20 parts of DMF, adding the diluted isocyanate curing agent into the step (1), stirring for 2 hours at 30 ℃ at 700 r/min, and filtering by a 400-mesh double-layer filter screen to obtain a base solution;
(3) coating the substrate solution on the release surface of the PET single-sided silicon release film at the speed of 10m/min, putting the PET single-sided silicon release film into an 8-section drying oven with the length of 32m for curing and drying, wherein the temperature of 1-8 sections is respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a substrate layer with the thickness of 30-50 mu m, and carrying out corona treatment on the substrate layer until 60 dynes are obtained;
(4) dissolving polybutylene succinate with the formula amount by 40 parts of DMF;
(5) diluting the isocyanate curing agent with the formula amount by 10 parts of DMF, adding into the step (4), stirring for 50min at 500 revolutions per minute, and filtering by a 500-mesh double-layer filter screen to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film at the speed of 30m/min, and putting the PET single-sided silicon release film into 8 sections of 32m drying ovens for curing and drying, wherein the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a pressure-sensitive adhesive layer with the thickness of 3-10 mu m;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
Example 2
The procedure is otherwise as in example 1, except that the isocyanate curing agent is used in an amount of 4 parts in the base layer.
Example 3
The procedure is otherwise as in example 1, except that the isocyanate curing agent is used in an amount of 6 parts in the base layer.
Example 4
The swelling adhesive tape for the degradable lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000071
Figure BDA0003261699870000081
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000082
the preparation method of the swelling adhesive tape for the degradable lithium ion battery comprises the following steps:
(1) dissolving polytrimethylene carbonate and polybutylene succinate in a formula amount by 100 parts of DMF;
(2) diluting amino resin curing agent and p-toluenesulfonic acid according to formula amount with 20 parts of DMF, adding into the step (1), stirring for 3h at 35 ℃ at 600 rpm, and filtering through a 300-mesh double-layer filter screen to obtain a base solution;
(3) coating the substrate solution on the release surface of the PET single-sided silicon release film at the speed of 10m/min, putting the PET single-sided silicon release film into an 8-section drying oven with the length of 32m for curing and drying, wherein the temperature of 1-8 sections is respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a substrate layer with the thickness of 30-50 mu m, and carrying out corona treatment on the substrate layer until 60 dynes are obtained;
(4) dissolving polybutylene succinate with the formula amount by 40 parts of DMF;
(5) diluting the amino resin curing agent and the p-toluenesulfonic acid in the formula amount by 10 parts of DMF, adding into the step (4), stirring at 600 rpm for 40min, and filtering by a 400-mesh double-layer filter screen to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film at the speed of 35m/min, and putting the PET single-sided silicon release film into 8 sections of 32m drying ovens for curing and drying, wherein the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a pressure-sensitive adhesive layer with the thickness of 3-10 mu m;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
Example 5
The procedure is as in example 4 except that the curing agent for the amino resin is used in an amount of 4 parts in the base layer.
Example 6
The procedure is as in example 4 except that the curing agent for the amino resin is used in an amount of 6 parts in the base layer.
Example 7
The swelling adhesive tape for the degradable lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000091
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
10 parts of polybutylene succinate;
0.5 part of isocyanate curing agent;
and 50 parts of DMF.
The preparation method of the swelling adhesive tape for the degradable lithium ion battery comprises the following steps:
(1) dissolving polylactic acid and poly butylene succinate in a formula amount by 100 parts of DMF;
(2) diluting the isocyanate curing agent with the formula amount by 20 parts of DMF, adding into the step (1), stirring for 2h at 30 ℃ at 700 r/min, and filtering by a 400-mesh double-layer filter screen to obtain a base solution;
(3) coating the substrate solution on the release surface of the PET single-sided silicon release film at the speed of 10m/min, putting the PET single-sided silicon release film into an 8-section drying oven with the length of 32m for curing and drying, wherein the temperature of 1-8 sections is respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a substrate layer with the thickness of 30-50 mu m, and carrying out corona treatment on the substrate layer until 60 dynes are obtained;
(4) dissolving polybutylene succinate with the formula amount by 40 parts of DMF;
(5) diluting the isocyanate curing agent with the formula amount by 10 parts of DMF, adding into the step (4), stirring for 50min at 500 revolutions per minute, and filtering by a 500-mesh double-layer filter screen to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film at the speed of 30m/min, and allowing the PET single-sided silicon release film to enter 8 sections of drying ovens of 32m for curing and drying, wherein the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a pressure-sensitive adhesive layer with the thickness of 3-10 mu m;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
Example 8
The swelling adhesive tape for the degradable lithium ion battery comprises a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
Figure BDA0003261699870000101
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
10 parts of polybutylene succinate;
0.5 part of isocyanate curing agent;
and 50 parts of DMF.
The preparation method of the swelling adhesive tape for the degradable lithium ion battery comprises the following steps:
(1) dissolving polycaprolactone and poly (butylene succinate) in a formula amount by 100 parts of DMF;
(2) diluting the isocyanate curing agent with the formula amount by 20 parts of DMF, adding the diluted isocyanate curing agent into the step (1), stirring for 2 hours at 30 ℃ at 700 r/min, and filtering by a 400-mesh double-layer filter screen to obtain a base solution;
(3) coating the substrate solution on the release surface of the PET single-sided silicon release film at the speed of 10m/min, putting the PET single-sided silicon release film into an 8-section drying oven with the length of 32m for curing and drying, wherein the temperature of 1-8 sections is respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a substrate layer with the thickness of 30-50 mu m, and carrying out corona treatment on the substrate layer until 60 dynes are obtained;
(4) dissolving polybutylene succinate with the formula amount by 40 parts of DMF;
(5) diluting the isocyanate curing agent with the formula amount by 10 parts of DMF, adding into the step (4), stirring for 50min at 500 revolutions per minute, and filtering by a 500-mesh double-layer filter screen to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film at the speed of 30m/min, and putting the PET single-sided silicon release film into 8 sections of 32m drying ovens for curing and drying, wherein the temperatures of 1-8 sections are respectively 90 ℃, 110 ℃, 120 ℃, 130 ℃, 145 ℃, 155 ℃, 110 ℃ and 90 ℃, so as to obtain a pressure-sensitive adhesive layer with the thickness of 3-10 mu m;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
Comparative example 1
The procedure of example 1 was repeated except that the isocyanate curing agent was used in an amount of 1 part in the base layer.
Comparative example 2
The procedure of example 1 was repeated except that the isocyanate curing agent was used in an amount of 10 parts in the base layer.
Comparative example 3
The procedure is as in example 4 except that the curing agent for the amino resin is used in an amount of 10 parts in the base layer.
The swelling tapes for degradable lithium ion batteries in the above examples and comparative examples were tested for steel plate peeling force, tape thickness, and swelling value in electrolytes at different temperatures.
The test method for the peeling force of the steel plate refers to the GB/T2792-2014 standard.
The total thickness test method refers to GB/T7125-.
The test method for swelling at 45 ℃ is as follows: 1) the total thickness h0 of the reference GB/T7125-; 2) cutting the test sample into 5cm by 5cm size to prepare 5 pieces; 3) putting the cut adhesive tape into a PE bottle, pouring electrolyte into the PE bottle to immerse a sample, and baking the PE bottle for 36 hours at the temperature of 45 ℃; 4) then taking out the sample, flattening the sample, testing the length a and the width b (unit is cm) of the sample by using a 30cm steel ruler, and simultaneously testing the thickness h of the sample after soaking and baking the sample by referring to the GB/T7125-2014 standard1(ii) a 5) Swelling ratio ═ a × b × h1/(25h0)*100％。
The test method of swelling at 50 ℃ is the same as the test method of swelling at 45 ℃ except that the baking temperature and time in step 3) are changed to baking at 50 ℃ for 96 hours.
The test method of swelling at 60 ℃ is the same as the test method of swelling at 45 ℃ except that the baking temperature and time in step 3) are changed to baking at 60 ℃ for 48 hours.
The test method of swelling at 85 ℃ is the same as the test method of swelling at 45 ℃ except that the baking temperature and time in step 3) are changed to baking at 85 ℃ for 4 hours.
The design of different temperature and time for swelling at 45-60 ℃ is designed by referring to the commonly used formation baking temperature of a cylindrical battery manufacturer, and belongs to the simulated actual use environment of a client; swelling at 85 ℃ is an evaluation of rapid detection during production.
The results of the above tests are shown in table 1.
TABLE 1
Figure BDA0003261699870000121
Figure BDA0003261699870000131
The swelling adhesive tape for the degradable lithium ion battery in each embodiment of the invention can realize effective swelling in SG202C1 of the Shengge energy science and technology company of Anhui, cylindrical battery electrolyte used by Jiangsu Haidao, cylindrical battery electrolyte used by Liaoning Jiuyi and cylindrical battery electrolyte used by Changhong Sanjie, can realize effective fixation of a battery core and a cylindrical shell of the cylindrical battery, and avoids damage to the battery caused by vibration or impact.
The above detailed description of the swelling tape for degradable lithium ion battery and the preparation method thereof with reference to the embodiments is illustrative and not restrictive, and several embodiments can be enumerated within the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. The swelling adhesive tape for the degradable lithium ion battery is characterized by comprising a substrate layer and a pressure-sensitive adhesive layer, wherein the substrate layer comprises the following raw materials in parts by weight:
30-50 parts of polytrimethylene carbonate;
30-50 parts of polybutylene succinate;
2-8 parts of a curing agent;
0-1.5 parts of a catalyst;
100 portions and 120 portions of solvent;
the pressure-sensitive adhesive layer comprises the following raw materials in parts by weight:
8-12 parts of polybutylene succinate;
0.3-0.8 part of curing agent;
0-0.05 part of catalyst;
45-55 parts of a solvent.
2. The swelling tape for degradable lithium ion batteries according to claim 1, wherein the polytrimethylene carbonate in the substrate layer is replaced by any one or two of polylactic acid and polycaprolactone; or, the polytrimethylene carbonate in the substrate layer is replaced with a combination of polytrimethylene carbonate and any two or three of polylactic acid and polycaprolactone.
3. The swelling tape for degradable lithium ion batteries according to claim 1 or 2, wherein the molecular weight of the polytrimethylene carbonate, the polylactic acid, the polycaprolactone and the polybutylene succinate is 6-20 ten thousand.
4. The swelling tape for degradable lithium ion batteries according to claim 1, wherein the curing agent is an isocyanate curing agent or an amino resin curing agent.
5. The swelling tape for degradable lithium ion batteries according to claim 4, wherein when the curing agent is an isocyanate curing agent, the amount of the catalyst is 0.
6. The swelling tape for degradable lithium ion batteries according to claim 4, wherein when the curing agent is an amino resin curing agent, the catalyst is p-toluenesulfonic acid; in the base layer, the mass ratio of the amino resin curing agent to the p-toluenesulfonic acid is 2-8: 1; in the pressure-sensitive adhesive layer, the mass ratio of the amino resin curing agent to the p-toluenesulfonic acid is 45-55: 1.
7. The swelling tape for degradable lithium ion batteries according to claim 1 or 2, wherein the solvent is N, N-dimethylformamide or ethyl acetate.
8. The swelling tape for degradable lithium ion batteries according to claim 1 or 2, wherein the thickness of the substrate layer is 30-50 μm, and the thickness of the pressure sensitive adhesive layer is 3-10 μm.
9. The method for preparing the swelling tape for degradable lithium ion batteries according to any one of claims 1 and 4 to 6, wherein the preparation method comprises the following steps:
(1) dissolving 30-50 parts of polytrimethylene carbonate and 30-50 parts of polybutylene succinate in a solvent;
(2) diluting 2-8 parts of curing agent and 0-1.5 parts of catalyst by using a solvent, adding into the step (1), uniformly stirring, and filtering to obtain a base solution;
(3) coating the substrate liquid on the release surface of the PET single-sided silicon release film, curing and drying to obtain a substrate layer, and carrying out corona treatment on the substrate layer;
(4) dissolving 8-12 parts of poly (butylene succinate) by using a solvent;
(5) diluting 0.3-0.8 part of curing agent and 0-0.05 part of catalyst by using a solvent, adding into the step (4), uniformly stirring, and filtering to obtain a pressure-sensitive adhesive liquid;
(6) coating the pressure-sensitive adhesive liquid on the release surface of the PET single-sided silicon release film, and curing and drying to obtain a pressure-sensitive adhesive layer;
(7) and (4) compounding the substrate layer obtained in the step (3) with the pressure-sensitive adhesive layer obtained in the step (6) to obtain the swelling adhesive tape for the degradable lithium ion battery.
10. The preparation method according to claim 9, wherein the thickness of the PET single-sided silicon release film is 15 to 30 μm; the dyne value of the base layer after corona treatment is greater than or equal to 52 dyne.
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CN106833449A (en) * 2017-02-13 2017-06-13 深圳市壹零壹工业设计有限公司 A kind of biodegradable polydactyl acid adhesive tape and preparation method thereof
CN108899579A (en) * 2018-06-14 2018-11-27 北京工业大学 A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute
CN212174869U (en) * 2020-04-09 2020-12-18 芜湖徽氏新材料科技有限公司 Special swelling adhesive tape for high-temperature-resistant lithium battery
CN212199101U (en) * 2019-10-29 2020-12-22 江苏丰远新材料科技有限公司 Degradable adhesive tape base film
CN112175191A (en) * 2020-09-22 2021-01-05 中山大学 Novel crosslinkable degradable multi-block copolymer and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106574036A (en) * 2014-06-11 2017-04-19 德莎欧洲公司 Polyester polyurethane
CN106833449A (en) * 2017-02-13 2017-06-13 深圳市壹零壹工业设计有限公司 A kind of biodegradable polydactyl acid adhesive tape and preparation method thereof
CN108899579A (en) * 2018-06-14 2018-11-27 北京工业大学 A kind of all-solid lithium-ion battery of self-crosslinking composite solid electrolyte prepared and its constitute
CN212199101U (en) * 2019-10-29 2020-12-22 江苏丰远新材料科技有限公司 Degradable adhesive tape base film
CN212174869U (en) * 2020-04-09 2020-12-18 芜湖徽氏新材料科技有限公司 Special swelling adhesive tape for high-temperature-resistant lithium battery
CN112175191A (en) * 2020-09-22 2021-01-05 中山大学 Novel crosslinkable degradable multi-block copolymer and preparation method and application thereof

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