CN115519870A - High-barrier aluminum plastic film for lithium battery flexible package, high-barrier adhesive and preparation method of high-barrier adhesive - Google Patents
High-barrier aluminum plastic film for lithium battery flexible package, high-barrier adhesive and preparation method of high-barrier adhesive Download PDFInfo
- Publication number
- CN115519870A CN115519870A CN202211480098.6A CN202211480098A CN115519870A CN 115519870 A CN115519870 A CN 115519870A CN 202211480098 A CN202211480098 A CN 202211480098A CN 115519870 A CN115519870 A CN 115519870A
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- Prior art keywords
- barrier
- barrier adhesive
- component
- film
- plastic film
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Links
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Images
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- H01M50/145—Primary casings; Jackets or wrappings for protecting against damage caused by external factors for protecting against corrosion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7246—Water vapor barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
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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
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Abstract
The invention relates to the technical field of lithium battery manufacturing, and discloses a high-barrier aluminum-plastic film for a lithium battery flexible package, a high-barrier adhesive and a preparation method thereof, wherein the high-barrier aluminum-plastic film comprises a PA film layer, a metal aluminum foil layer and a PP film layer, and high-barrier adhesive coatings with the thickness of 10-30 mu m are respectively arranged between the metal aluminum foil layer and the PA and PP film layers; the coatings are all formed into a multi-scale and multi-layer microcosmic three-dimensional elastic network structure by interweaving irregular particles, columnar protrusions and irregular pores and mutually and stably connecting all the parts in the thickness direction, and the diameter of the pores penetrating through all the layers in the thickness direction of the microcosmic three-dimensional elastic network structure is less than 0.3nm, so that the high-barrier aluminum plastic film for the lithium battery flexible package, which can resist oxygen and water vapor permeation, is formed. According to the invention, the 3D network microstructure and the low-nanometer-level pores are formed through the components of the adhesive, so that the aluminum-plastic film has higher peeling force and high barrier property, and the manufacturing requirements of the aluminum-plastic film used for power lithium batteries and the like are met.
Description
Technical Field
The invention relates to the field of lithium battery manufacturing, in particular to a high-barrier aluminum-plastic film for a lithium battery flexible package, a high-barrier adhesive and a preparation method thereof.
Background
In recent years, under the environmental protection requirement and the promotion of national policy, new energy vehicles develop rapidly, and meanwhile, as a power source of new energy vehicles, lithium ion batteries develop particularly rapidly in these years, and there are three common structures of lithium batteries: soft-packaged battery cell, cylinder battery cell and square battery cell. The soft package battery has the advantages of good safety performance, light weight, large capacity, small internal resistance, changeable shape, flexible design and the like, and is widely applied to new energy automobiles.
The soft-packaged battery is generally packaged by an aluminum-plastic film, can play a good role in sealing and protection, and can protect the battery from normal operation. However, due to the high technical barrier of the aluminum plastic film, the domestic aluminum plastic film market is monopolized by foreign enterprises for a long time, and the domestic production rate is about 10%. The aluminum plastic film for the lithium battery must have good heat sealing, insulating and mechanical properties, and must also have excellent insulating properties against water and oxygen in the air, and have extremely high stability against corrosive electrolytes inside the battery. Due to the requirements of high mechanical property, high isolation, high corrosion resistance and the like of the aluminum plastic film of the soft package battery, the adhesive in the prior art cannot meet the requirements at the same time. In order to enable the aluminum plastic film to meet the above-mentioned overall performance requirements, the aluminum plastic film is generally implemented by increasing the number of laminated layers of the aluminum plastic film or increasing the thickness between the coatings, and such a technical scheme results in a complex manufacturing process and high material cost on one hand, and significantly increases the overall thickness and mass of the aluminum plastic film, which is not favorable for increasing the energy density (including the mass energy density and the volumetric energy density) of the lithium battery. For example, the conventional invention document CN 105070854A discloses a lithium battery composite packaging high-barrier aluminum-plastic film and a preparation method thereof, the aluminum-plastic film is formed by sequentially laminating a copolymerized propylene layer, a first adhesive layer, a terephthalic acid resin layer, a second adhesive layer, a metal oxide film layer, an aluminum foil layer, a third adhesive layer, a nylon layer and a fluorine coating layer from inside to outside. The heat-sealing layer of the aluminum plastic film effectively increases the barrier property and the chemical stability of the inner layer by adding the terephthalic acid resin layer.
In the prior art, the invention patent document CN 108517194A discloses a two-component solvent-free polyurethane adhesive special for a high-barrier aluminum-plastic material and a preparation method thereof, wherein the two-component solvent-free polyurethane adhesive special for the high-barrier aluminum-plastic material is prepared from an adhesive a and an adhesive B, wherein the adhesive a takes polyether glycol, TDI, IPDI and hexamethylene diisocyanate trimer as raw materials; the adhesive B takes dimer acid, polyhydric alcohol, 1, 3-butanediol, sebacic acid and isophthalic acid as raw materials, and tetrabutyl titanate as a catalyst to obtain polyester polyol with specific acid value and hydroxyl value; then mixing polyester polyol, polyether polyol and hydroxyl-terminated polybutadiene to prepare glue B; mixing the glue A and the glue B with a mixing ratio of 10. The glue has good bonding fastness for high-barrier aluminum-plastic materials, but the glue cannot remarkably improve the barrier property of the aluminum-plastic materials, and particularly cannot effectively isolate water vapor and oxygen in the air.
Therefore, in the lithium battery aluminum plastic film and the adhesive in the prior art, the prepared aluminum plastic film is difficult to be taken into consideration, and the insulation performance of the aluminum plastic film to water vapor and oxygen in the air cannot be effectively improved on the premise of not increasing the thickness and the number of film layers of the aluminum plastic film on the basis of good flexibility, tensile resistance, hydrolysis resistance, heat resistance, cohesiveness, impact resistance and the like; meanwhile, the preparation method has the defects of complex preparation process, more components, high cost and the like; in particular, the adhesive cannot directly improve the adhesive to provide good oxygen and water vapor barrier performance for the aluminum plastic film.
Disclosure of Invention
In order to overcome the defects existing in the prior art, the invention aims to provide a high-barrier adhesive for a lithium battery aluminum plastic film and a preparation method thereof, wherein components, a formula and a preparation process of the adhesive are simultaneously improved, and a coating structure with a unique microstructure is formed through the cooperative matching of the components, so that all parts of each coating structure are mutually and stably connected to form a multi-scale and multi-layer three-dimensional elastic network structure, and the diameter of a pore penetrating through each layer in the thickness direction of the three-dimensional elastic network structure is less than 0.3nm, so that the high-barrier lithium battery aluminum plastic film for resisting oxygen and water vapor permeation is formed, the gas (especially oxygen) barrier property of the aluminum plastic film is obviously improved, the water vapor is almost completely prevented from entering, and the service life of the lithium battery is prolonged; meanwhile, the invention simplifies the material components and the preparation process, does not need to increase the overall thickness of the coating and the aluminum-plastic film, and does not influence the energy density of the lithium battery.
In order to achieve the purpose, the invention provides the following technical scheme:
a lithium battery flexible package high barrier aluminum-plastic film is characterized in that: the composite film comprises a PA film layer, a metal aluminum foil layer and a PP film layer which are sequentially stacked, wherein a first high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PA film layer, and a second high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PP film layer; the first high-barrier adhesive coating and the second high-barrier adhesive coating are formed by uniformly coating high-barrier adhesives between two layers of materials; the high-barrier adhesive comprises a component A and a component B, wherein the component A and the component B are mixed and then react, and then are uniformly coated between a metal aluminum foil and a PA film or a PP film to respectively form a first high-barrier adhesive coating and a second high-barrier adhesive coating with the thickness of 10-30 micrometers, gaps between the metal aluminum foil and the PA film or the PP film are respectively filled with the coatings, irregular particles, columnar protrusions and irregular pores are interwoven in at least the thickness direction of each coating, all the coatings are mutually and stably connected to form a multi-scale and multi-layer microscopic three-dimensional elastic network structure, and the diameters of the pores penetrating through all the layers in the thickness direction of the microscopic three-dimensional elastic network structure are smaller than 0.3nm, so that the high-barrier aluminum plastic film for lithium battery flexible packaging capable of blocking oxygen and water vapor permeation is formed.
The microcosmic three-dimensional elastic network structure of each coating comprises a plurality of approximately spongy local structure units which are mutually overlapped and connected in the thickness direction and the length direction and are formed by irregular columnar protrusions and irregular pores in the micrometer scale and the nanometer scale, the local structure units are mutually connected in the three-dimensional space of the coating, under the combined action of physical action and intermolecular action, a plurality of layers of elastic 3D network connections are formed, and the diameter of the pores penetrating through each layer in the thickness direction and the length direction is smaller than 0.3nm.
The shape of the irregular particles forming each local structural unit is approximately spherical, the diameter range of the irregular particles is 10 to 50 nm, the shape of the irregular columnar protrusions is approximately mastoid, and the diameter range of the irregular columnar protrusions is 50 to 1200 nm; the diameter range of irregular pores formed between adjacent irregular particles and the columnar protrusions is 0.1 to 800nm, and the diameters of the pores between layers are reduced through intermolecular action, so that the diameters of the pores penetrating through all layers are smaller than 0.3nm.
The high-barrier adhesive is used for preparing the high-barrier aluminum plastic film for the flexible packaging of the lithium battery, and comprises a hydroxyl-terminated polyurethane resin serving as a component A and a polyisocyanate curing agent serving as a component B, wherein the mass ratio of the component A to the component B is 100: (5 to 20), reacting, and uniformly coating the mixture between a metal aluminum foil and a PA (polyamide) film or a PP (polypropylene) film to respectively form a first high-barrier adhesive coating and a second high-barrier adhesive coating which are 10 to 30 micrometers in thickness and have the microscopic three-dimensional elastic network structure.
The polyisocyanate curing agent as the component B is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, TDI-TMP adduct, HDI trimer, HDI biuret, carbodiimide-modified MDI, liquefied MDI, etc.
The hydroxyl-terminated polyurethane resin serving as the component A is prepared by taking hydrophobic polyol and polyester polyol as raw material components, dehydrating the raw material components under the vacuum environment of 110 to 120 ℃ and over-0.095 MPa, adding polyisocyanate and a catalyst, reacting the mixture under the vacuum environment of 80 to 85 ℃, adding a chain extender, a cross-linking agent and a diluent, and carrying out polymerization reaction.
The hydrophobic polyol is one or more of hydroxyl-terminated polybutadiene, cardela cashew nut shell oil polyol NX-9203, NX-9203LP, dow VORAPEL series hydrophobic polyether polyol and the like.
The polyester polyol is one or more of polycaprolactone dihydric alcohol, polycaprolactone trihydric alcohol, poly hexanediol adipate diol, poly butanediol adipate diol, polycarbonate triol and the like.
The preparation method of the high-barrier adhesive is characterized by comprising the following steps:
s1: respectively preparing a component A and a component B;
s2: and (A): the component B comprises the following components in a mass ratio of 100: and (5) to 20) mixing and reacting, and uniformly stirring to prepare the high-barrier adhesive.
Compared with the prior art, the invention can at least realize the following beneficial effects:
1. according to the high-barrier aluminum-plastic film for the lithium battery flexible package, the coating with the unique microscopic three-dimensional elastic network structure is respectively constructed among the PA film layer, the metal aluminum foil layer and the PP film layer by introducing the high-barrier adhesive, the coating structure with the unique microscopic structure is formed by the cooperative matching of the components, all parts of each coating structure are mutually and stably connected to form the multi-scale (nano and micron) and multi-layer three-dimensional elastic network structure, the diameter of a pore penetrating through each layer in the thickness direction of the network three-dimensional elastic structure is less than 0.3nm, less than 0.346nm of the diameter of an oxygen molecule and 0.4nm of the diameter of a water molecule, so that the high-barrier aluminum-plastic film for the lithium battery resisting the permeation of oxygen and water vapor is formed, the gas (especially oxygen) barrier property of the aluminum-plastic film is remarkably improved, and the oxygen and water vapor can be almost completely prevented from penetrating through the aluminum-plastic film to enter the lithium battery, so that the service life of the lithium battery is prolonged.
2. The lithium battery flexible package high-barrier aluminum-plastic film and the high-barrier adhesive provided by the invention form a unique microscopic coating structure by improving the adhesive and introducing high-polarity groups such as strong-polarity carbamido groups and ester groups, so that the prepared aluminum-plastic film overcomes the technical contradiction between the layer number and the thickness of a film material and the requirement of comprehensive performance, and can provide good oxygen and water vapor barrier performance for the aluminum-plastic film by directly improving the adhesive, therefore, on the basis of enabling the aluminum-plastic film to have good flexibility, stretch resistance, hydrolysis resistance, heat resistance, cohesiveness, impact resistance and the like, the barrier performance of the aluminum-plastic film to water vapor and oxygen in the air can be effectively improved on the premise of not increasing the thickness and the film number of the aluminum-plastic film, a unique 3D network three-dimensional elastic structure is formed in the coating, the pore diameters penetrating through all layers in the coating thickness and length directions are smaller than 0.3nm and smaller than the diameters of oxygen molecules and water molecules, so that oxygen molecules and water molecules invading into the film coating can not penetrate through the layers in the thickness direction, the length direction of the film coating, and the energy of the lithium battery can not be synchronously increased, and the comprehensive barrier performance of the lithium battery can not be increased.
3. The high-barrier adhesive and the preparation method thereof provided by the invention simplify the material components and the preparation process, and overcome the defects of complex preparation process, more components, high cost and the like in the prior art. According to the high-barrier adhesive provided by the invention, hydroxyl-terminated polyurethane resin is synthesized, and high-polarity groups such as hydrophobic molecular chains, strong-polarity carbamido groups and ester groups are introduced into the resin, so that a 3D network three-dimensional elastic structure finally formed after a polymer is cured in a coating has strong hydrophobicity, the diameters of pores penetrating through all layers in the coating thickness and length directions are smaller than 0.3nm and smaller than the diameters of oxygen molecules and water molecules, and oxygen and water vapor in air are not easy to permeate into the coating.
4. According to the lithium battery flexible package high-barrier aluminum-plastic film and the high-barrier adhesive, strong intermolecular attraction is formed among main chain molecules of the adhesive through introduced strong polar groups such as carbamido groups and ester groups, free spaces among polymer chains are reduced, oxygen and water vapor molecules are difficult to move in a coating after the adhesive is cured, and the oxygen and water vapor molecules are difficult to move or penetrate in the thickness direction and the length direction, so that the high-efficiency and reliable oxygen and water vapor barrier effect is achieved, and the failure of the barrier property caused by the deformation of a local microstructure of the coating can be avoided.
5. The invention provides a high-barrier aluminum-plastic film for a lithium battery flexible package and a high-barrier adhesive, which are characterized in that the components, the formula and the preparation process of the adhesive are improved simultaneously, strong-polarity carbamido groups, ester groups and other groups with high polarity are introduced, so that the components are matched with each other to form a unique microscopic local structural unit and then are connected with each other to form a coating, the coating is tightly combined with a PA film layer, a metal aluminum foil layer and a PP film layer on the basis, and double-layer coatings on two sides of an aluminum foil improve the gas barrier property of the aluminum-plastic film integrally through physical action and intermolecular combined action to prevent oxygen and water vapor from entering the coating and further prevent the oxygen and the water vapor from penetrating into the lithium battery through the coating. The invention solves the problem that the existing adhesive can not directly isolate the aluminum-plastic film from oxygen and water vapor efficiently and reliably, can obviously improve the sealing effect of the aluminum-plastic film for the lithium battery and other packaging film materials, reduces the thickness of the film materials and the aluminum foil, makes up the possibility of sealing failure caused by the defects of materials such as the aluminum foil, a sealing layer and the like and physical connection, and provides reliable guarantee for the sealing performance of the aluminum-plastic film and the packaging material thereof.
6. According to the aluminum plastic film and other packaging materials prepared by the high-barrier adhesive, the components of the adhesive in the coating, the formed 3D network microstructure and the low-nanometer-level through pores enable the aluminum plastic film to have good flexibility, adhesion, hydrolysis resistance, electrolyte corrosion resistance and other properties, the high-barrier adhesive can also be widely used for adhesion of other metal foils and organic material films such as nylon and the like, has high stripping force and high barrier property, and can better meet the manufacturing requirements of aluminum plastic films and the like used by power lithium batteries and the like; through actual tests, the main performances such as the barrier performance and the like of the composite material meet or are superior to the requirements of the prior art standard.
Drawings
Other objects and results of the present invention will become more apparent and more readily appreciated by reference to the following description taken in conjunction with the accompanying drawings, and as the invention is more fully understood.
FIG. 1 is a SEM diagram of a high-barrier adhesive coating of an embodiment of the invention at a 40 μm scale;
FIG. 2 is a SEM diagram of a high-barrier adhesive coating of an embodiment of the invention at a 20 μm scale;
FIG. 3 is a SEM illustration of a 5 μm scale high barrier adhesive coating in accordance with an embodiment of the invention;
FIG. 4 is a SEM illustration of a high-barrier adhesive coating of an embodiment of the invention at a 4 μm scale;
FIG. 5 is a SEM image of a high-barrier adhesive coating of an embodiment of the invention at a dimension of 500 nm;
fig. 6 is a SEM schematic view of a high-barrier adhesive coating according to an embodiment of the present invention at a 400nm scale.
Detailed Description
Referring to fig. 1 to fig. 6, the technical solution of the present invention is described in detail by using a plurality of embodiments.
Examples
The lithium battery flexible package high-barrier aluminum plastic film provided in this embodiment is specifically applicable to the manufacture of a ternary polymer lithium ion power battery with a flexible package, such as lithium nickel manganese cobalt (Li (NiCoMn) O) 2 ) Lithium nickel cobalt aluminate, lithium cobalt oxide and other systems.
The high-barrier aluminum-plastic film for the flexible package of the lithium battery comprises a PA film layer, a metal aluminum foil layer and a PP film layer which are sequentially stacked, wherein a first high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PA film layer, and a second high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PP film layer; the first high-barrier adhesive coating and the second high-barrier adhesive coating are formed by uniformly coating high-barrier adhesives between two layers of materials; the high-barrier adhesive comprises a component A and a component B, wherein the component A and the component B are mixed and then react, and then are uniformly coated between a metal aluminum foil and a PA film or a PP film to respectively form a first high-barrier adhesive coating and a second high-barrier adhesive coating with the thickness of 10-30 micrometers, gaps between the metal aluminum foil and the PA film or the PP film are respectively filled with the coatings, irregular particles, columnar protrusions and irregular pores are interwoven in the thickness direction and the length direction of each coating, all parts are mutually and stably connected to form a multi-scale and multi-layer microscopic three-dimensional elastic network structure, and the diameters of the pores penetrating through all layers in the thickness direction of the microscopic three-dimensional elastic structure are smaller than 0.3nm, so that the high-barrier aluminum plastic film for the lithium battery flexible package capable of resisting oxygen and water vapor permeation is formed.
The microcosmic three-dimensional elastic network structure of each coating comprises a plurality of approximately spongy local structure units which are mutually overlapped and connected in the thickness direction and the length direction, wherein the approximately spongy local structure units are respectively formed by irregular columnar protrusions and irregular pores in the micrometer scale and the nanometer scale, the scales and the shapes of the local structure units are not completely consistent but are similar to each other, the structures and the distribution are random and irregular, but the local structure units are mutually connected in a three-dimensional space in the coating, the outward surfaces of the local structure units are connected with the surfaces of a PA film layer, a metal aluminum foil layer and a PP film layer, and the local structure units form a multilayer elastic 3D network connection under the combined action of physical action and intermolecular action, so that the microcosmic three-dimensional elastic network structure has better flexible deformation capability, and the diameters of the pores penetrating through each layer are smaller than 0.3nm in the thickness direction and the length direction.
The shape of the irregular particles forming each local structural unit is approximately spherical, the diameter range of the irregular particles is 10 to 50 nm, the shape of the irregular columnar protrusions is approximately mastoid, and the diameter range of the irregular columnar protrusions is 50 to 1200 nm; the diameter range of irregular pores formed between adjacent irregular particles and the columnar protrusions is 0.1-800nm, and the diameters of the pores between layers are reduced through intermolecular action, so that the diameters of the pores penetrating through all layers are smaller than 0.3nm.
A high-barrier adhesive is used for preparing the high-barrier aluminum-plastic film for the flexible packaging of the lithium battery, and comprises hydroxyl-terminated polyurethane resin serving as a component A and a polyisocyanate curing agent serving as a component B, wherein the mass ratio of the component A to the component B is 100: (5-20), reacting, and uniformly coating the mixture between a metal aluminum foil and a PA film or a PP film to form a first high-barrier adhesive coating and a second high-barrier adhesive coating which are 10-30 mu m thick and have the microscopic three-dimensional elastic network structure respectively.
The polyisocyanate curing agent as the component B is one or a mixture of more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, TDI-TMP adduct, HDI trimer, HDI biuret, carbodiimide-modified MDI, liquefied MDI, etc.
The hydroxyl-terminated polyurethane resin serving as the component A is prepared by taking hydrophobic polyol and polyester polyol as raw material components, dehydrating at the temperature of 110 to 120 ℃ and under the vacuum environment of more than-0.095 MPa, adding polyisocyanate and a catalyst, reacting at the temperature of 80 to 85 ℃, adding a chain extender, a cross-linking agent and a diluent, and carrying out polymerization reaction.
The hydrophobic polyol is one or more of hydroxyl-terminated polybutadiene, cardela cashew nut shell oil polyol NX-9203, NX-9203LP, dow VORAPEL series hydrophobic polyether polyol and the like.
The polyester polyol is one or more of polycaprolactone dihydric alcohol, polycaprolactone trihydric alcohol, poly adipate hexanediol diol, poly adipate butanediol diol, polycarbonate triol and the like.
The catalyst is one or more of dibutyltin dilaurate, stannous octoate, bismuth neodecanoate, zinc isooctanoate and the like; the chain extender and the cross-linking agent are as follows: one or more of HDI tripolymer, HDI biuret, 1, 4-butanediol, trimethylolpropane and the like; the diluent is as follows: one or more of butanone, ethyl acetate, methyl acetate, dimethyl carbonate, butyl acetate, etc.
A preparation method of a high-barrier adhesive comprises the following steps:
s1: respectively preparing a component A and a component B;
wherein, the step S1 specifically includes the following steps:
s11: putting 100 parts of hydrophobic polyol and 100 parts of polyester polyol into a reaction kettle, stirring, heating to 110-120 ℃, and dehydrating in vacuum for 2 hours under the vacuum environment of more than-0.095 MPa until the tested moisture content is less than or equal to 500ppm,
s12: cooling to 80-85 ℃, adding polyisocyanate for radical reaction, adding a catalyst after reacting for 30 minutes, adding a chain extender for chain extension and a crosslinking agent for crosslinking after reacting for 90 minutes, reacting for 120 minutes, and cooling to 50 ℃; in the step, firstly, the polyol and the polyisocyanate are subjected to radical reaction to ensure that isocyanate is arranged at two ends of the polyol, and then the polyol chain extender is added for chain extension;
s13: and adding 400 parts of diluent, discharging after the polymerization reaction is completed, and sealing and storing to obtain the component A, namely the hydroxyl-terminated polyurethane resin.
S2: and (A): the component B comprises the following components in a mass ratio of 100: (5-20), uniformly stirring, and after the polymerization reaction is finished, preparing the high-barrier adhesive.
According to actual needs, can also evenly exert pressure to lithium cell flexible packaging high resistant separation plastic-aluminum membrane in the thickness direction, to the first high resistant separation gluing agent coating that sets up between metal aluminium foil layer and the PA rete, the second high resistant separation gluing agent coating that sets up between metal aluminium foil layer and the PP rete, carry out the physics compaction, strengthen each local constitutional unit in each coating and in physical action and intermolecular action, make the multilayer elasticity 3D network connection that it formed, have better flexible deformability, littleer hole, make microcosmic three-dimensional elasticity network structure on thickness and length direction, all can make the hole diameter that pierces through each layer all be less than 0.3nm, effective separation oxygen, steam gets into in the coating and is the hole between coating and other retes.
Referring to the attached drawings 1-6, in each high-barrier adhesive coating of the embodiment of the invention, the components of the high-barrier adhesive form a multi-scale and multi-layer microcosmic three-dimensional elastic network structure formed by interweaving irregular particles, columnar protrusions and irregular pores in the thickness direction and stably connecting all parts, and the diameters of pores penetrating through all layers in the thickness direction of the microcosmic three-dimensional elastic network structure are less than 0.3nm, so that the high-barrier aluminum plastic film for the flexible packaging of the lithium battery, which can resist the permeation of oxygen and water vapor, is formed.
Example 1
The high-barrier aluminum plastic film for the lithium battery flexible package, the high-barrier adhesive and the preparation method thereof provided by the embodiment are further refined on the basis of the embodiment 1. The difference lies in that:
the hydroxyl-terminated polyurethane resin as the component A comprises the following components in proportion and a preparation method thereof:
putting 100 parts of hydroxyl-terminated butadiene and 100 parts of polycaprolactone diol into a reaction kettle, stirring, heating to 120 ℃, dehydrating for 2 hours in vacuum at the pressure of more than-0.095 MPa until the moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 25 parts of isophorone diisocyanate, reacting for 30 minutes, adding 0.5 part of dibutyltin dilaurate, reacting for 90 minutes, adding 2.5 parts of crosslinking agent trihydroxymethane, reacting for 120 minutes, cooling to 50 ℃, adding 200 parts of diluent ethyl acetate and 200 parts of butyl acetate, discharging, sealing and storing to obtain hydroxyl-terminated polyurethane resin;
the preparation method of the high-barrier adhesive comprises the following steps:
and (A): the component B is mixed and uniformly stirred according to the mass ratio of 100 to 15, and the high-barrier adhesive is obtained after the polymerization reaction is finished; wherein the component B curing agent is HDI tripolymer.
Example 2
The high-barrier aluminum plastic film for the lithium battery flexible package, the high-barrier adhesive and the preparation method thereof provided by the embodiment are further refined on the basis of the embodiment 1. The difference lies in that:
the hydroxyl-terminated polyurethane resin as the component A comprises the following components in proportion and a preparation method thereof:
putting 100 parts of Kandelia cashew shell oil polyol NX-9203 and 100 parts of polycarbonate triol into a reaction kettle, stirring and heating to 120 ℃, dehydrating in vacuum for 2 hours at the pressure of-0.095 MPa till the tested moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 33 parts of hexamethylene diisocyanate, reacting for 30 minutes, adding 1.5 parts of bismuth neodecanoate, reacting for 90 minutes, adding 1, 4-butanediol and 3.3 parts, reacting for 120 minutes, cooling to 50 ℃, adding 370 parts of diluent butanone and 100 parts of dimethyl carbonate, discharging, sealing and storing to obtain hydroxyl-terminated polyurethane resin;
the preparation method of the high-barrier adhesive comprises the following steps:
and (A): the component B is mixed and uniformly stirred according to the mass ratio of 100:8, and the high-barrier adhesive is obtained after the polymerization reaction is finished; wherein the component B curing agent is: TDI-TMP adducts.
Example 3
The high-barrier aluminum plastic film for the lithium battery flexible package, the high-barrier adhesive and the preparation method thereof provided by the embodiment are further refined on the basis of the embodiment 1. The difference lies in that:
the hydroxyl-terminated polyurethane resin as the component A comprises the following components in proportion and a preparation method thereof:
putting 120 parts of hydroxyl-terminated polybutadiene, 30 parts of poly hexanediol adipate diol and 50 parts of polycarbonate triol into a reaction kettle, stirring and heating to 120 ℃, dehydrating for 2 hours in vacuum at the pressure of more than-0.095 MPa until the tested moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 36 parts of diphenylmethane diisocyanate, adding 0.8 part of dibutyltin dilaurate after reacting for 30 minutes, adding 1.3 parts of trimethylolpropane and 4.5 parts of HDI trimer after reacting for 90 minutes, cooling to 50 ℃, adding 210 parts of methyl acetate serving as a diluent and 230 parts of butanone, discharging, and sealing and storing to obtain the hydroxyl-terminated polyurethane resin.
The preparation method of the high-barrier adhesive comprises the following steps:
and (A): the component B is mixed and uniformly stirred according to the mass ratio of 100: 20, and the high-barrier adhesive is obtained after the polymerization reaction is finished; wherein, the component B curing agent is: carbodiimide modified MDI.
Example 4
The high-barrier aluminum plastic film for the lithium battery flexible package, the high-barrier adhesive and the preparation method thereof provided by the embodiment are further refined on the basis of the embodiment 1. The difference lies in that:
putting 80 parts of hydroxyl-terminated polybutadiene, 60 parts of polybutylene adipate glycol and 60 parts of Dow VORAPEL WT5000 polyether polyol into a reaction kettle, stirring, heating to 120 ℃, performing vacuum dehydration for 2 hours at the pressure of more than-0.095 MPa until the tested moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 42 parts of diphenylmethane diisocyanate, adding stannous octoate after reacting for 30 minutes, adding 2 parts of 1, 4-butanediol, 2 parts of HDI biuret after reacting for 90 minutes, reacting for 120 minutes, cooling to 50 ℃, adding 450 parts of ethyl acetate serving as a diluent, discharging, and storing in a sealed manner to obtain hydroxyl-terminated polyurethane resin;
the preparation method of the high-barrier adhesive comprises the following steps:
and (A): the component B is mixed and stirred uniformly according to the mass ratio of 100: 5, and the high-barrier adhesive is obtained after the polymerization reaction is finished; wherein, the component B curing agent is: liquefying MDI.
Example 5
The high-barrier aluminum plastic film for the lithium battery flexible package, the high-barrier adhesive and the preparation method thereof provided by the embodiment are further refined on the basis of the embodiment 1. The difference lies in that:
the component A is hydroxyl-terminated polyurethane resin and the preparation method thereof comprises the following steps:
40 parts of Kandelia cashew shell oil polyol NX-9203LP, 90 parts of polyhexamethylene adipate glycol, 70 parts of polycaprolactone triol are put into a reaction kettle, stirred and heated to 120 ℃, and vacuum dehydrated for 2 hours at the pressure of-0.095 MPa until the moisture content is less than or equal to 500ppm, the temperature is reduced to 80 ℃, 21 parts of toluene diisocyanate is added, after 30 minutes of reaction, zinc isooctanoate is added for 4 parts, after 90 minutes of reaction, HDI biuret is added for 8 parts, the reaction time is 120 minutes, the temperature is reduced to 50 ℃,120 parts of diluent butanone, 100 parts of butyl acetate and 100 parts of ethyl acetate are added, and the hydroxyl-terminated polyurethane resin is obtained after discharging, sealing and storage.
The preparation method of the high-barrier adhesive comprises the following steps:
and (A): the component B is mixed and uniformly stirred according to the mass ratio of 100 to 14, and the high-barrier adhesive is obtained after the polymerization reaction is finished; the component B curing agent is: TDI-TMP adducts.
Comparative example 1:
the component A is hydroxyl-terminated polyurethane resin and the preparation method thereof comprises the following steps:
putting 200 parts of polyether glycol PPG-2000 into a reaction kettle, stirring, heating to 120 ℃, dehydrating for 2 hours in vacuum at the pressure of-0.095 MPa or above until the moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 24 parts of toluene diisocyanate, reacting for 30 minutes, adding 0.5 part of dibutyltin dilaurate, reacting for 90 minutes, adding 4 parts of 1, 4-butanediol, reacting for 120 minutes, cooling to 50 ℃, adding 120 parts of butanone serving as a diluent and 330 parts of ethyl acetate, discharging, and sealing and storing to obtain hydroxyl-terminated polyurethane resin;
the component B curing agent is: TDI-TMP adducts;
and (A): and (3) mixing the component B according to the mass ratio of 100 to 13, and uniformly stirring to obtain the adhesive for the aluminum-plastic film in the comparative example 1.
Comparative example two:
the component A is hydroxyl-terminated polyurethane resin and the preparation method thereof comprises the following steps:
putting 140 parts of polyhexamethylene glycol adipate diol and 60 parts of polycarbonate triol into a reaction kettle, stirring, heating to 120 ℃, dehydrating under vacuum at the pressure of more than-0.095 MPa for 2h until the tested moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 31 parts of isophorone diisocyanate, reacting for 30 minutes, adding 1.5 parts of dibutyltin dilaurate and reacting for 90 minutes, adding 1, 4-butanediol, 2 parts of trimethylolpropane and 3 parts of trimethylolpropane, reacting for 120 minutes, cooling to 50 ℃, adding 220 parts of butyl acetate serving as a diluent and 160 parts of ethyl acetate, discharging, sealing and storing to obtain hydroxyl-terminated polyurethane resin;
the component B curing agent is: HDI trimer;
and (A): and mixing the component B according to the mass ratio of 100 to 8, and uniformly stirring to obtain the adhesive for the aluminum-plastic film of the comparison 2.
Comparative example three:
the component A hydroxyl-terminated polyurethane resin and the preparation method thereof are as follows:
putting 90 parts of polycaprolactone triol and 90 parts of PPG-2000 into a reaction kettle, stirring, heating to 120 ℃ at the pressure of above-0.095 MPa, dehydrating under vacuum for 2h until the moisture content is less than or equal to 500ppm, cooling to 80 ℃, adding 34 parts of hexamethylene diisocyanate, reacting for 30 minutes, adding 2.5 parts of stannous octoate, reacting for 90 minutes, adding 3 parts of trimethylolpropane and 3 parts of HDI biuret, reacting for 120 minutes, cooling to 50 ℃, adding 150 parts of dimethyl carbonate serving as a diluent and 230 parts of ethyl acetate, discharging, and sealing for storage to obtain hydroxyl-terminated polyurethane resin;
the component B comprises a curing agent: HDI tripolymer;
and (A): and (3) mixing the component B according to the mass ratio of 100 to 17, and uniformly stirring to obtain the adhesive for the aluminum-plastic film of the comparative 2.
Comparative testing and evaluation
The adhesive for the aluminum-plastic film prepared in each embodiment and the comparative example is respectively coated among the PA film layer, the metal aluminum foil layer and the PP film layer to form a coating with the thickness of 10 microns, the aluminum-plastic film with the total thickness of less than 25 microns is prepared, and then the main performance parameters of the aluminum-plastic film are tested.
The performance evaluation method comprises the following steps:
and (3) testing the peel strength: testing according to GB/T2791-1995 adhesive T peel strength test method;
oxygen permeability test: testing is carried out according to the coulometer detection method for oxygen permeability test of plastic films and thin sheets of packaging materials GB/T19789-2005;
water vapor permeability test: testing according to GB1037-88 test method for water vapor permeability of plastic film and sheet;
the results of the performance tests of the inventive and comparative examples are shown in the following table:
the test results show that when the thickness of the coating is 10 mu m, the water vapor transmission capacity of the adhesive and the aluminum-plastic film prepared by the embodiments of the invention is less than 4.2 g/(m) 2 24 h); in general, a 25 μm film is used in the industry, and has a moisture permeability of less than 5 g/(m) 2 24 h) is called a high moisture-resistant packaging material, and the moisture permeability is 5 to 20 g/(m) 2 24 h) moisture-barrier packaging materials with a moisture permeability of > 20 g/(m) 2 24 h) is called low moisture barrier packaging material. The water vapor transmission capacity of the aluminum plastic film prepared by the embodiments of the invention can meet or exceed the water vapor transmission standard requirement of the high moisture resistance packaging material, and the comparative examples can not meet the requirement.
At a coating thickness of 10 μm, the oxygen transmission coefficient is < 3.2cm 3 .mm/(m 2 24 h.MPa) and will have a permeability coefficient for oxygen of < 3.8cm internationally 3 .mm/(m 2 24h.mpa) polymer, referred to as barrier polymer. The oxygen permeability of the high-barrier adhesive and the aluminum-plastic film prepared by the embodiments of the invention reaches or is superior to the standard of the high-barrier packaging material; and the respective proportions cannot meet the requirements.
It should be noted that, within the scope of the components, ratios and process parameters described in the present invention, other components, ratios and process parameters can be selected to achieve the technical effects of the present invention, and therefore, the present invention is not listed in the present invention.
In summary, the above embodiments of the present invention are focused on introducing strong polar groups such as urea groups and ester groups into the adhesive, so that the adhesive has excellent hydrophobic properties, and when a coating is formed, strong intermolecular attraction is formed between the strong polar groups such as urea groups and ester groups on the main chain of the adhesive, so that local structural units with different dimensions and close connection can be formed together with physical action, pores between the local structural units are reduced, and meanwhile, the adhesive provides good adhesion to substrates such as nylon and aluminum foil, and the aluminum plastic film has excellent electrolyte resistance, water resistance, oxygen and water vapor isolation properties, so as to prolong the service life of the lithium battery. The aluminum-plastic film prepared by the invention does not need to increase the overall thickness of a coating or a film material, and avoids influencing other core properties such as energy density of a lithium battery on the basis of providing the comprehensive properties of the aluminum-plastic film, thereby realizing dialectical unification of quality improvement, efficiency improvement and cost reduction.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention should be included in the protection scope of the invention.
Claims (11)
1. A lithium battery flexible package high barrier aluminum-plastic film is characterized in that: the composite film comprises a PA film layer, a metal aluminum foil layer and a PP film layer which are sequentially stacked, wherein a first high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PA film layer, and a second high-barrier adhesive coating is arranged between the metal aluminum foil layer and the PP film layer; the first high-barrier adhesive coating and the second high-barrier adhesive coating are formed by uniformly coating high-barrier adhesives between two layers of materials; the high-barrier adhesive comprises a component A and a component B, wherein the component A and the component B are mixed and then react, and then are uniformly coated between a metal aluminum foil and a PA film or a PP film to respectively form a first high-barrier adhesive coating and a second high-barrier adhesive coating with the thickness of 10-30 micrometers, gaps between the metal aluminum foil and the PA film or the PP film are respectively filled with the coatings, irregular particles, columnar protrusions and irregular pores are interwoven in the thickness direction, all parts are mutually and stably connected to form a multi-scale and multi-layer microscopic three-dimensional elastic network structure, and the diameters of the pores penetrating through all layers in the thickness direction of the microscopic three-dimensional elastic network structure are smaller than 0.3nm, so that the lithium battery flexible packaging high-barrier aluminum plastic film capable of blocking oxygen and water vapor permeation is formed.
2. The high barrier aluminum plastic film for the flexible package of lithium batteries as claimed in claim 1, wherein: the microcosmic three-dimensional elastic network structure of each coating comprises a plurality of local structural units which are mutually overlapped and connected and are approximately spongy and formed by irregular columnar protrusions and irregular pores on the micrometer scale and the nanometer scale in the thickness and length directions, the local structural units are mutually connected in the three-dimensional space of the coating, under the combined action of physical action and intermolecular action, a plurality of layers of elastic 3D network connections are formed, and the diameter of the pores penetrating through each layer is smaller than 0.3nm in the thickness and length directions.
3. The high-barrier aluminum-plastic film for the flexible package of the lithium battery as claimed in claim 2, wherein: the shape of the irregular particles forming each local structure unit is approximately spherical, the diameter range of the irregular particles is 10 to 50 nm, the shape of the irregular columnar protrusions is approximately mastoid, and the diameter range of the irregular columnar protrusions is 50 to 1200 nm; the diameter range of irregular pores formed between adjacent irregular particles and the columnar protrusions is 0.1 to 800nm, and the diameters of the pores between layers are reduced through intermolecular action, so that the diameters of the pores penetrating through all layers are smaller than 0.3nm.
4. A high-barrier adhesive is used for preparing the lithium battery flexible package high-barrier aluminum-plastic film as claimed in any one of claims 1 to 3, and comprises hydroxyl-terminated polyurethane resin as a component A and a polyisocyanate curing agent as a component B, wherein the mass ratio of the component A to the component B is 100: (5 to 20), reacting, and uniformly coating the mixture between a metal aluminum foil and a PA (polyamide) film or a PP (polypropylene) film to respectively form a first high-barrier adhesive coating and a second high-barrier adhesive coating which are 10 to 30 micrometers in thickness and have the microscopic three-dimensional elastic network structure.
5. The high-barrier adhesive according to claim 4, wherein the polyisocyanate curing agent serving as the component B is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, TDI-TMP adduct, HDI trimer, HDI biuret, carbodiimide-modified MDI, or liquefied MDI.
6. The high-barrier adhesive according to claim 4, wherein the hydroxyl-terminated polyurethane resin as the component A is prepared by taking hydrophobic polyol and polyester polyol as raw material components, dehydrating the raw material components under a vacuum environment of 110 to 120 ℃ and over-0.095 MPa, adding polyisocyanate and a catalyst into the raw material components, reacting the mixture at 80 to 85 ℃, adding a chain extender, a cross-linking agent and a diluent into the reaction product, and performing polymerization reaction.
7. The high-barrier adhesive according to claim 6, wherein the hydrophobic polyol is one or more of hydroxyl-terminated polybutadiene, cardela cashew nut shell oil polyol NX-9203, NX-9203LP, and Dow VORAPEL series hydrophobic polyether polyol.
8. The high-barrier adhesive as claimed in claim 6, wherein the polyester polyol is one or more of polycaprolactone diol, polycaprolactone triol, polyhexamethylene adipate diol, polybutylene adipate diol, polycarbonate diol and polycarbonate triol.
9. The high-barrier adhesive as claimed in claim 6, wherein the catalyst is one or more of dibutyltin dilaurate, stannous octoate, bismuth neodecanoate and zinc isooctanoate; the chain extender and the cross-linking agent are as follows: one or more of HDI tripolymer, HDI biuret, 1, 4-butanediol and trimethylolpropane; the diluent is as follows: one or more of butanone, ethyl acetate, methyl acetate, dimethyl carbonate and butyl acetate.
10. The preparation method of the high-barrier adhesive is characterized by comprising the following steps:
s1: respectively preparing a component A and a component B;
s2: and (A): the component B comprises the following components in a mass ratio of 100: (5-20) and stirring uniformly to obtain the high-barrier adhesive according to any one of claims 4-9.
11. The preparation method of the high-barrier adhesive according to claim 10, wherein the step S1 specifically comprises the following steps:
s11: putting hydrophobic polyol and polyester polyol into a reaction kettle, stirring, heating to 110 to 120 ℃, and dehydrating in vacuum for 2 hours under the vacuum environment of more than-0.095 MPa until the test moisture content is less than or equal to 500ppm;
s12: cooling to 80 to 85 ℃, adding polyisocyanate to perform a radical reaction, adding a catalyst after the reaction is performed for 30 minutes, adding a chain extender and a cross-linking agent after the reaction is performed for 90 minutes, reacting for 120 minutes, and cooling to 50 ℃;
s13: and adding 400 parts of diluent, discharging after the polymerization reaction is completed, and sealing and storing to obtain the component A hydroxyl terminated polyurethane resin.
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| CN112208167A (en) * | 2020-10-20 | 2021-01-12 | 安徽双津实业有限公司 | Aluminum-plastic film for lithium battery packaging |
| CN113956832A (en) * | 2021-11-29 | 2022-01-21 | 韦尔通(厦门)科技股份有限公司 | Double-component PU (polyurethane) structural adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112208167A (en) * | 2020-10-20 | 2021-01-12 | 安徽双津实业有限公司 | Aluminum-plastic film for lithium battery packaging |
| CN113956832A (en) * | 2021-11-29 | 2022-01-21 | 韦尔通(厦门)科技股份有限公司 | Double-component PU (polyurethane) structural adhesive and preparation method thereof |
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| Title |
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| 《中国鞋业大全》编委会: "《中国鞋业大全》", 30 January 1998 * |
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