CN110571365A - External packing material for lithium ion battery and application thereof - Google Patents

External packing material for lithium ion battery and application thereof Download PDF

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Publication number
CN110571365A
CN110571365A CN201910654913.8A CN201910654913A CN110571365A CN 110571365 A CN110571365 A CN 110571365A CN 201910654913 A CN201910654913 A CN 201910654913A CN 110571365 A CN110571365 A CN 110571365A
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China
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layer
aluminum foil
lithium ion
resin film
treatment liquid
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CN201910654913.8A
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CN110571365B (en
Inventor
赵金保
符琼
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Xiamen University
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Xiamen University
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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/116—Primary casings; Jackets or wrappings characterised by the material
    • H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
    • H01M50/1245—Primary casings; Jackets or wrappings characterised by the material having a layered structure characterised by the external coating on the casing
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • 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
    • 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
    • B32B2307/536—Hardness
    • 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
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The invention discloses an external packing material for a lithium ion battery and application thereof, wherein the material sequentially comprises a heat-resistant resin film outer layer, an aluminum foil layer and a thermoplastic resin film inner layer from outside to inside; at least one surface of the aluminum foil layer is chemically treated and comprises an organic matter layer and an oxidation layer, the organic matter layer is formed by treating an aluminum foil through a first treatment liquid, and the first treatment liquid is a chromium-free treatment liquid comprising a coupling agent, organic acid or organic acid salt and aqueous resin; the oxide layer is formed by degreasing and passivating the aluminum foil; solves the problems of cracking, whitening and layering of the outer packaging material for the lithium ion battery during deep drawing and heat sealing.

Description

External packing material for lithium ion battery and application thereof
Technical Field
The invention relates to an outer packaging material for a lithium ion battery and application thereof.
Background
In recent years, small and lightweight lithium ion batteries, also called lithium secondary batteries, have been developed as power storage devices used in portable terminal devices such as personal computers and mobile phones, cameras, satellites, vehicles, and the like, and have a structure including: a battery body composed of a positive electrode current collector/a positive electrode active material layer/a separator/an electrolyte layer/a negative electrode active material layer/a negative electrode current collector, and an exterior material for lithium ion battery, which encloses the battery body. The outer package material for lithium ion batteries is formed by laminating inner and outer resin films and an aluminum foil, wherein the aluminum foil and the inner and outer films are bonded by an adhesive. Unlike conventional metal cans used as containers for battery elements, the cans are excellent in performance such as light weight, high heat dissipation, and high flexibility in shape.
The outer packaging material for the lithium ion battery is manufactured and molded by the following method: a recess is formed in a part of the outer package for a lithium ion battery by deep drawing or a bulging method, the battery body is accommodated in the recess, the remaining part where no recess is formed is folded back, and the edge part is thermally fused and sealed with the tab extending from the positive electrode and the negative electrode interposed therebetween. The following problems mainly exist in the actual production process of the outer packaging material for the lithium ion battery: firstly, in order to improve the energy density of the lithium ion battery, a deeper concave part is required to be formed, but when a metal mold is used for forming, an outer layer film or an aluminum foil is easy to crack and whiten at a corner with high stretching rate; secondly, in order to realize the tightness of the outer packaging material for the lithium ion battery, high-temperature hot melting is adopted to melt and bond the inner layer resin, but the outer layer shrinks due to high temperature, and delamination occurs when the shrinkage force is larger than the bonding strength of the outer layer film and the aluminum foil.
The problems are solved, the properties of the adhesive and the inner and outer layers are closely related, the surface treatment of the aluminum foil is not separated, and the surface adhesive force of the aluminum foil and the adhesive strength of the aluminum foil and the inner and outer layer films are improved on the one hand, and the corrosion resistance, the flexibility and the hardness of the aluminum foil are improved on the other hand through a proper treatment method.
At present, the surface treatment of aluminum foil is carried out by passivating hexavalent chromium and trivalent chromium solutions, and the treatment method is applied to the aluminum foil treatment of lithium ion battery packaging, so that a packaging film material with excellent performance can be obtained, but waste liquid generated in the treatment process contains heavy metal ions such as chromium, manganese and cobalt and substances such as phosphoric acid and hydrofluoric acid which seriously pollute the environment. Researches show that the peeling strength of the aluminum foil and the plastic film is effectively improved by compounding the aluminum foil subjected to silanization treatment and the plastic film, but the problems of cracking and layering existing in deep punching and heat sealing of the outer packaging material for the lithium ion battery are not solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an outer packaging material for a lithium ion battery and application thereof, and solves the problems of cracking, whitening and layering of the outer packaging material for the lithium ion battery in the background technology during deep drawing and heat sealing.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the outer packaging material for the lithium ion battery comprises a heat-resistant resin film outer layer, an aluminum foil layer and a thermoplastic resin film inner layer from outside to inside in sequence; a bonding agent layer is also arranged between the outer layer of the heat-resistant resin film and the aluminum foil layer;
in a preferred embodiment of the present invention, an adhesive layer is also disposed between the aluminum foil layer and the inner layer of the thermoplastic resin film.
First, regarding the heat-resistant resin film outer layer:
The outer layer of the heat-resistant resin film is a stretched polyester resin film or a nylon film, and the thickness of the heat-resistant resin film is 20-100 micrometers; wherein the polyester resin film is selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester and polycarbonate; the nylon film is made of polyamide resin, including nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 6,10, and poly (m-xylylene adipamide), and preferably has a melting point higher than that of the thermoplastic resin film constituting the inner layer, so that the heat-resistant resin film of the outer layer is not adversely affected when heat-sealing is performed. The heat-resistant resin film outer layer is a member that plays a role of preventing the occurrence of fracture due to necking of the aluminum foil during molding, and contains one or more layers of heat-resistant resin films. And the heat-resistant resin film can be subjected to an easy-adhesion treatment such as plasma treatment, ozone treatment, corona discharge treatment, undercoating treatment, and the like.
Second, regarding the adhesive layer:
The adhesive layer is a dry laminating adhesive with the thickness of 1-10 mu m and is arranged between the outer layer of the heat-resistant resin film and the organic matter layer.
As the binder constituting the binder layer, a polyurethane-based binder in which a bifunctional or higher isocyanate compound is reacted with a main agent such as polyester polyol, polyether polyol, acrylic polyol, and carbonate polyol is preferable.
Examples of the polyester polyol include polyester polyols obtained by polymerizing a diol and a dibasic acid compound.
Examples of the dibasic acid include: aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dibasic acids such as isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid. These dibasic acids may be used alone or in combination of two or more.
Examples of the diol include: aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol, alicyclic diols such as cyclohexanediol and hydrogenated benzenedimethanol, and aromatic diols such as benzenedimethanol. These diols may be used alone or in combination of two or more.
As the polyester polyol, a polyurethane polyol in which the terminal hydroxyl group of the polyester polyol is reacted with an isocyanate compound to produce a polyester type can be used.
Examples of the isocyanate compound include: 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, xylylene diisocyanate, 4,4 '-diphenylmethane diisocyanate, methylene diisocyanate, isopropene diisocyanate, lysine diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, methylcyclo diisocyanate, isophorone diisocyanate, 4, 4' -dicyclohexylmethane diisocyanate, and the like.
These isocyanate compounds may be used as monomers, or as adducts, biuret compounds and isocyanurate compounds composed of the isocyanate compounds.
examples of the polyether polyol include ether polyols such as polyethylene glycol and polypropylene glycol. In addition, a polyether type polyurethane polyol obtained by reacting the above isocyanate compound with the ether polyol can also be used.
Examples of the acrylic polyol include acrylic resins obtained by polymerizing acrylic ester monomers.
Examples of the carbonate polyol include polyols obtained by reacting a carbonate compound with a diol compound.
Examples of the carbonate compound include: dimethyl carbonate, diphenyl carbonate, ethylene carbonate, and the like. The diol compound may be a diol compound forming the polyester polyol, and a polycarbonate-type polyurethane polyol obtained by reacting the isocyanate compound with the carbonate polyol may be used.
And thirdly, regarding the aluminum foil layer:
As the metal foil layer of the exterior material for lithium ion batteries, the aluminum foil functions to prevent moisture and oxygen from entering the interior of the exterior material for lithium ion batteries. In order to prevent the aluminum foil from being broken or pin-holed during the molding process, the aluminum foil is preferably made of a soft aluminum foil having a thickness of 10 to 80 μm, more preferably 15 to 40 μm, and when the aluminum foil has a thickness of 80 μm or less, the effect of improving the breakage during the molding and the effect of generating pin-holes can be maintained, and the total thickness of the outer packaging material for a lithium ion battery is not too large, and the increase in weight and the decrease in energy density can be prevented.
The outer side surface of the aluminum foil layer is chemically treated to form a first chemical treatment layer, and the first chemical treatment layer comprises an organic matter layer and an oxidation layer from outside to inside; the thickness of the first chemical treatment layer is 2-15 mu m, wherein the thickness of the oxidation layer is 1-5 mu m, and the thickness of the organic matter layer is 1-10 mu m.
The organic matter layer is formed by treating an aluminum foil with a first treatment liquid, the first treatment liquid comprises, by mass, 0.1-5% of a coupling agent, 1-10% of an organic acid or an organic acid salt, 0.5-20% of a water-based resin and the balance of water, the pH of the solution is not less than 7, and the pH of the solution is adjusted by using sodium hydroxide and ammonia water. Under the condition of room temperature, the method is carried out by roller coating, soaking, brush coating and other modes; after the first treatment liquid is prepared, the first treatment liquid is placed at room temperature for more than 24 hours for use; in order to ensure the solution to be uniformly mixed in the preparation process, homogenization treatment can be carried out by means of means not limited to magnetic stirring, ultrasound and the like.
The organic layer and the heat-resistant resin film outer layer are laminated through an adhesive, the first chemical treatment layer applied to the surface of the aluminum foil enables the bonding strength of the aluminum foil and the adhesive layer to be more stable, and on the other hand, the corrosion resistance, the flexibility and the hardness of the aluminum foil are improved, so that the outer packaging material for the lithium ion battery is prevented from cracking or layering during forming processing and heat sealing.
The coupling agent is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent, organic acid such as organic sulfonic acid, carboxylic acid, sulfinic acid, thiocarboxylic acid and the like, and organic acid salt such as metal or nonmetal salt of the above organic acid. The cross-linked network structure is formed on the oxide layer on the surface of the aluminum foil through the cross-linking effect of the coupling agent, and simultaneously, the organic acid or the organic acid salt is added, so that the formed organic layer interface is more stable under the combined action of the coupling agent and the organic acid salt, the density of functional groups such as hydroxyl, amino, carboxyl and the like which have reactivity to the adhesive is increased, the bonding strength between the surface of the aluminum foil and the inner and outer layer films is favorably improved, and the outer layer film is not easy to peel off from the surface of the aluminum foil during high-temperature heat sealing.
By adding at least one water-based resin into the chromium-free treatment liquid, wherein the water-based resin specifically comprises water-based resin and emulsion-type resin, such as water-based acrylic emulsion/resin, water-based polyurethane emulsion/resin, organic silicon resin/emulsion, water-based alkyd resin, amino resin, epoxy resin/emulsion, polyester resin, polyurethane acrylic hybrid and the like, the problem that an outer layer film or an aluminum foil cracks at a corner with high tensile rate during forming processing is solved, the invasion of moisture to the surface of the aluminum foil is inhibited, the flexibility and the mechanical strength of the aluminum foil are improved, the coupling agent is uniformly distributed on an oxide layer, the compactness of a film layer is improved, and the problem that the outer layer film or the aluminum foil cracks.
The oxide layer is formed by degreasing and passivating the aluminum foil; degreasing treatment is carried out by using a conventional organic solvent such as acetone, carbon tetrachloride and xylene, an alkaline cleaning solution such as an aqueous solution containing sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium silicate and the like, electrolytic pickling treatment, acid activation treatment and the like, passivation treatment is carried out to replace a loose and unstable oxide film of the aluminum foil, a layer of stably existing oxide layer is formed on the surface of the aluminum foil, and usable treatment methods such as an anodic oxidation method, passivation solution treatment of concentrated nitric acid, concentrated sulfuric acid, titanozonate, rare earth metal salt, molybdate, organic phytic acid and the like, high-temperature chemical treatment and the like are available.
In a preferred embodiment of the present invention, the aluminum foil further comprises a second chemical treatment layer, the second chemical treatment layer is disposed between the aluminum foil layer and the thermoplastic resin film inner layer, has a thickness of 1nm to 30 μm, and is formed by treating the aluminum foil with a second treatment liquid, and the second treatment liquid is a chromium-containing treatment liquid or a chromium-free treatment liquid identical to the first treatment liquid.
The second chemical treatment layer serves to firmly adhere the thermoplastic resin film to the aluminum foil layer, prevent delamination due to hydrogen fluoride generated from the electrolyte solution and hydrolysis of the electrolyte solution, and prevent delamination of the exterior material for a lithium ion battery during processing. The chemical treatment layer 5 is formed on the surface of the aluminum foil by treatment with a treatment liquid containing chromium or no chromium, chromium-containing treatments such as chromate treatment, phosphate treatment and coating-type chromate treatment, and non-chromium treatments such as titanzirconate treatment, molybdate treatment, silicate treatment, etc. The chemical treatment layer 5 may comprise or be identical to the chemical treatment layer 3 according to actual production requirements. The chemical treatment layer 5 is preferably formed by a coating type treatment in view of the bonding fastness to the aluminum foil 4 and the inner layer 6 and the ability to be continuously processed without washing with water to obtain low processing cost.
Fourthly, regarding the thermoplastic resin film inner layer:
the thermoplastic resin film inner layer is formed by polyolefin, is an unstretched film of polypropylene, maleic acid modified polypropylene, ethylene-acrylate copolymer or ionomer resin, and has a thickness of 10-100 mu m. The inner layer constituting the outer covering material for lithium ion batteries is constituted of at least a thermoplastic resin film, and the thermoplastic resin film used for the inner layer is selected as needed, but is preferably a thermoplastic resin film which has heat sealability, can exert an effect of improving resistance to corrosive lithium ion battery electrolytes and the like, and ensures insulation between the aluminum foil and the positive and negative electrodes of the battery main body, and is preferably an unstretched polyolefin film such as polypropylene, maleic acid-modified polypropylene and the like, and an unstretched film such as an ethylene-acrylic acid ester copolymer or an ionomer resin and these films may be appropriately combined and multilayered. The thermoplastic resin film and the aluminum foil in the inner layer may be laminated by hot extrusion or dry lamination, and examples of the adhesive include acid-modified olefin adhesives, acrylic adhesives, styrene elastomer adhesives, silicone adhesives, ether adhesives, and ethylene-vinyl acetate adhesives.
In a preferred embodiment of the present invention, the thickness of the inner layer of the thermoplastic resin film is 25 to 100 μm.
The second technical scheme adopted by the invention for solving the technical problems is as follows: provides an application of an outer packaging material for a lithium ion battery, in particular to an application in the preparation of the lithium ion battery.
In a preferred embodiment of the present invention, the outer packaging material for a lithium ion battery is heat-cured, then a concave portion is formed by deep drawing or bulging, the battery body is accommodated in the concave portion, the remaining portion where no concave portion is formed is folded, and the edge portion is heat-sealed for 1 to 30 seconds at a temperature of 150 to 230 ℃ and under a pressure of 0.1 to 1MPa with a tab extending between the positive electrode and the negative electrode of the battery interposed therebetween.
Compared with the background technology, the technical scheme has the following advantages:
At least one side of the aluminum foil layer is chemically treated, and the organic matter layer is formed by treating the treatment solution containing the coupling agent, the organic acid or organic acid salt and the aqueous resin, so that the bonding strength between the surface of the aluminum foil and the inner and outer films is improved, and the outer film is not easy to peel off from the surface of the aluminum foil during high-temperature heat sealing to generate a layering phenomenon; meanwhile, the thickness selection and the surface treatment mode of the aluminum foil are combined, so that the flexibility and the hardness of the aluminum foil are effectively improved, the uniformity and the quality of a surface film layer of the aluminum foil are improved, and the problem that an outer film or the aluminum foil is cracked at corners with high stretching rate during forming and processing is solved. The external packaging material is used for preparing the lithium battery, can maintain the effect of improving fracture and the effect of generating pinholes when an aluminum foil is formed, solves the problems of cracking, whitening and layering during deep drawing and heat sealing in the preparation process, has not too thick total thickness, can prevent weight increase and energy density reduction, and is beneficial to volume reduction of the lithium battery.
Drawings
Fig. 1 is a sectional view of an exterior material for a lithium ion battery according to the present invention.
FIG. 2 is a schematic drawing of the deep drawing process of the outer packaging material for lithium ion batteries according to the present invention.
FIG. 3 is a schematic diagram of heat-sealing formation in the process of preparing a lithium ion battery according to the present invention
The heat-resistant composite material comprises a heat-resistant resin film 1-outer layer, a binder 2-layer, a first chemical treatment layer 3 '-organic matter layer, a 3' -oxide layer, a 4-aluminum foil, a second chemical treatment layer 5-and a thermoplastic resin film 6-inner layer.
Detailed Description
Example 1
The outer packaging material for the lithium ion battery comprises a heat-resistant resin film outer layer 1, a binder layer 2, an organic layer 3 ', an oxide layer 3', an aluminum foil 4, a second chemical treatment layer and a thermoplastic resin film inner layer 6 in sequence from outside to inside;
The surface of an aluminum foil 4 is degreased with acetone and passivated with concentrated nitric acid, the outer side surface of the aluminum foil 4 is treated with a chromium-free treatment solution containing an epoxy group silane coupling agent KH560, sodium citrate and an aqueous acrylic resin YZ-A01 (Xiamen Yizhou New energy Co., Ltd.) to form a first chemical treatment layer 3, a polyurethane adhesive (first adhesive layer 2) is coated on the first chemical treatment layer 3 by a gravure roll, after drying to some extent by heating, a biaxially stretched nylon film (heat-resistant resin film outer layer 1) having a thickness of 25 μm is laminated on the adhesive layer 2, and a thermoplastic resin film inner layer 6 is laminated on the other side surface of the aluminum foil 4 to form an exterior material for a lithium ion battery.
The lithium ion battery outer packaging material was aged at 75 ℃ for 3 days, the aged lithium ion battery outer packaging material was deep-drawn to form a concave portion, the battery body was housed in the concave portion, the remaining portion where no concave portion was formed was folded back, and the edge portion was heat-sealed under pressure at 200 ℃ and 1MPa for 10 seconds with the tab extending between the positive electrode and the negative electrode, and the inner layer 6 thermoplastic resin film was heat-fused and sealed.
example 2
Example 2 differs from example 1 in that: after the surface of the aluminum foil 4 was passivated by alkali cleaning to remove oil and concentrated sulfuric acid, the outer side surface of the aluminum foil 4 was treated with a chromium-free treatment solution containing a chelating titanate coupling agent KR238S, sodium gluconate and an aqueous acrylic resin YZ-a01 (xiamen yi boat new energy limited), to form a first chemical treatment layer 3, a polyurethane adhesive (first adhesive layer 2) was coated on the first chemical treatment layer 3 by a gravure roll, and after drying the same to some extent by heating, a biaxially stretched nylon film (heat-resistant resin film outer layer 1) having a thickness of 25 μm was laminated on the adhesive layer 2, and a thermoplastic resin film inner layer 6 was laminated on the other side surface of the aluminum foil 4, to form an exterior material for a lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
Example 3
Example 3 differs from example 1 in that: after the surface of an aluminum foil 4 is subjected to alkali cleaning degreasing and concentrated nitric acid passivation, the outer side surface of the aluminum foil 4 is treated with a chromium-free treatment solution containing an acyloxy group-containing silane coupling agent KH570, tartaric acid and an organic silicon emulsion to form a first chemical treatment layer 3, then a polyurethane-based adhesive (first adhesive layer 2) is coated on the first chemical treatment layer 3 by a gravure roll, after being dried to some extent by heating, a biaxially stretched nylon film (heat-resistant resin film outer layer 1) having a thickness of 25 μm is laminated on the adhesive layer 2, the other side surface of the aluminum foil 4 is subjected to oil removal such as alkali cleaning, and then a second chemical treatment layer 5 is formed by treatment with a chromate passivation treatment solution containing at least phosphoric acid and potassium dichromate, and then a thermoplastic resin film inner layer 6 is bonded on the second chemical treatment layer 5 to form an exterior material for a lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
Example 4
Example 4 differs from example 1 in that: after the surface of the aluminum foil 4 is subjected to alkali cleaning to remove oil and titanium zirconate passivation, the outer side surface of the aluminum foil 4 is treated with a chromium-free treatment solution containing aminosilane coupling agents KH550 and KH103, gluconic acid and sodium dodecylsulfate to form a first chemical treatment layer 3, then a polyurethane adhesive (a first adhesive layer 2) is coated on the first chemical treatment layer 3 by a gravure roll, after drying to some extent by heating, a biaxially stretched nylon film (a heat-resistant resin film outer layer 1) having a thickness of 40 μm is laminated on the adhesive layer 2, and the other side surface of the aluminum foil 4 is subjected to the same treatment as the outer side surface and then is bonded with a thermoplastic resin film inner layer 6 to form an exterior material for a lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
Example 5
Example 5 differs from example 1 in that: the surface of the aluminum foil 4 is degreased by acetone and passivated by concentrated nitric acid, the outer side surface of the aluminum foil 4 is treated by a chromium-free treatment liquid containing a silane coupling agent Si40, an aminosilane coupling agent KH550, sodium gluconate and a water-based polyurethane acrylic resin hybrid YZ-C04 (Xiamen Yizhou New energy Co., Ltd.) to form a first chemical treatment layer 3, then a polyurethane adhesive (a first adhesive layer 2) is coated on the first chemical treatment layer 3 by a gravure roll, after being dried to a certain degree by heating, a biaxial stretching nylon film with the thickness of 40 mu m is laminated on the adhesive layer 2, and a thermoplastic resin film inner layer 6 is attached to the other side surface of the aluminum foil 4, thereby forming the outer packaging material for the lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
Comparative example 1
After the surface of the aluminum foil 4 was passivated by alkali cleaning to remove oil and concentrated sulfuric acid, the outer side surface of the aluminum foil 4 was treated with a chromium-free treatment liquid containing a chelate type titanate coupling agent KR238S to form a first chemical treatment layer 3, a polyurethane-based adhesive (first adhesive layer 2) was coated on the first chemical treatment layer 3 by a gravure roll, and after drying to some extent by heating, a biaxially stretched nylon film having a thickness of 25 μm was laminated on the adhesive layer 2, and a thermoplastic resin film inner layer 6 was laminated on the other side surface of the aluminum foil 4 to form an exterior material for a lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
comparative example 2
After the surface of the aluminum foil 4 was degreased with acetone and passivated with concentrated nitric acid, the outer side surface of the aluminum foil 4 was treated with a chromium-free treatment solution containing sodium citrate and an aqueous acrylic resin YZ-a01 (xiamen yi boat new energy limited) to form a first chemical treatment layer 3, a polyurethane adhesive (the 1 st adhesive layer 2) was coated on the first chemical treatment layer 3 by a gravure roll, and after drying to some extent by heating, a biaxially stretched nylon film having a thickness of 25 μm was laminated on the adhesive layer 2, and a thermoplastic resin film inner layer 6 was laminated on the other side surface of the aluminum foil 4 to form an exterior material for a lithium ion battery.
The lithium ion battery was produced in the same manner as in example 1, and subjected to deep drawing and sealing.
First, evaluation of initial lamination Strength
the lithium ion battery outer packaging materials of examples 1 to 5 and comparative examples 1 to 2 produced by the above-described method were cut out according to the requirements of national standard 8808-1988, and rectangular samples 15mm × 200mm were prepared, and the outer layers of nylon and aluminum foil were peeled off at a speed of 100mm/min using a tensile tester, and the T-peel strength measured was taken as the initial lamination strength (unit: N/15mm) of nylon and aluminum foil, and the evaluation results for each sample are summarized in table 1.
As shown in Table 1, the initial lamination strength of the outer packaging materials of examples 1 to 5 and comparative examples 1 to 2 of the present invention was 7.0N/15mm or more, and the initial lamination strength of the outer packaging material of example 5 was 12N/15mm or more.
Second, evaluation of deep drawability
the exterior materials for lithium ion batteries of examples 1 to 5 and comparative examples 1 to 2 produced by the above method were cut out to prepare rectangular sheet samples of 90mm × 200mm, the rectangular sheets were pressed with a 45mm × 60mm metal mold at a pressure of 1MPa, the rectangular sheet samples were press-molded to a molding depth of 5mm, rectangular recesses of 45mm × 60mm having a depth of 5mm were produced with heat-seal portions left around the recesses, and whether or not the nylon or aluminum foil at the corners of each of the molding recesses was cracked or whitened was visually observed, and the results of evaluation of each sample were summarized in table 1.
As shown in table 1, nylon or aluminum foil at the corners of the recesses was not cracked or whitened during the deep drawing of the exterior materials of examples 1, 2, 3, 4, and 5 (o).
Third, evaluation of Heat sealability
The lithium ion battery outer materials of examples 1 to 5 and comparative examples 1 to 2, which were subjected to deep drawing, were sealed by folding back the remaining portions without forming the recesses and hot-melt bonding the edge portions for 10 seconds at a temperature of 200 ℃ and a pressure of 1MPa while sandwiching the tabs extending from the positive electrode and the negative electrode. The heat-sealed corners were visually observed for the occurrence of nylon peeling, and the results of evaluation of the respective samples are summarized in Table 1.
As shown in table 1, when the outer packaging materials of examples 1, 2, 3, 4 and 5 of the present invention were heat-sealed, the nylon did not peel off at the corners of the heat seals (o).
TABLE 1 evaluation of Performance of outer packaging Material for lithium ion Battery
As shown in table 1, the exterior material for lithium ion batteries according to the examples of the present invention exhibited good initial lamination strength, deep drawability, and heat sealability.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.

Claims (10)

1. An outer packaging material for a lithium ion battery, characterized in that: the heat-resistant aluminum foil comprises a heat-resistant resin film outer layer, an aluminum foil layer and a thermoplastic resin film inner layer from outside to inside in sequence; the outer side surface of the aluminum foil layer is chemically treated to form a first chemical treatment layer, the first chemical treatment layer comprises an organic matter layer and an oxidation layer from outside to inside, the organic matter layer is formed by treating an aluminum foil with a first treatment liquid, and the first treatment liquid is a chromium-free treatment liquid comprising a coupling agent, an organic acid or an organic acid salt and an aqueous resin; the oxide layer is formed by degreasing and passivating the aluminum foil; the thickness of the first chemical treatment layer is 2-15 mu m, the thickness of the oxidation layer is 1-5 mu m, and the thickness of the organic matter layer is 1-10 mu m.
2. The exterior material for lithium ion batteries according to claim 1, characterized in that: the first treatment solution consists of 0.1-5% of coupling agent, 1-10% of organic acid or organic acid salt, 0.5-20% of water-based resin and the balance of water by mass percent, wherein the pH value of the solution is more than or equal to 7.
3. The exterior material for lithium ion batteries according to claim 1, characterized in that: the coupling agent is at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent; the organic acid comprises organic sulfonic acid, carboxylic acid, sulfinic acid and thiocarboxylic acid, and the organic acid salt is a metal or nonmetal salt of the organic acid; the aqueous resin includes water-dispersible resins and emulsion-type resins.
4. The exterior material for lithium ion batteries according to claim 1, characterized in that: the aluminum foil is characterized by further comprising a second chemical treatment layer, wherein the second chemical treatment layer is arranged between the aluminum foil layer and the thermoplastic resin film inner layer, is 1 nm-30 mu m thick and is formed by treating the aluminum foil through a second treatment liquid, and the second treatment liquid is a chromium-containing treatment liquid or a chromium-free treatment liquid which is the same as the first treatment liquid.
5. The exterior material for lithium ion batteries according to claim 1, characterized in that: the adhesive layer is a dry laminating adhesive with the thickness of 1-10 mu m, and is arranged between the outer layer of the heat-resistant resin film and the organic layer and/or on the outer side surface of the inner layer of the thermoplastic resin film.
6. The exterior material for lithium ion batteries according to claim 1, characterized in that: the aluminum foil layer is a soft aluminum foil with the thickness of 10-80 mu m.
7. The exterior material for lithium ion batteries according to claim 1, characterized in that: the outer layer of the heat-resistant resin film is a stretched polyester resin film or a nylon film, and the thickness of the heat-resistant resin film is 20-100 micrometers; wherein the polyester resin film is selected from polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolyester and polycarbonate; the nylon membrane adopts polyamide resin, including nylon 6, nylon 66, copolymer of nylon 6 and nylon 66, nylon 6,10 and poly-m-xylene adipamide.
8. The exterior material for lithium ion batteries according to claim 1, characterized in that: the inner layer of the thermoplastic resin film is an unstretched film of polypropylene, maleic acid modified polypropylene, ethylene-acrylate copolymer or ionomer resin, and the thickness of the unstretched film is 10-100 mu m.
9. The exterior material for lithium ion batteries according to claim 1, characterized in that: the thickness of the thermoplastic resin film inner layer is 25-100 mu m.
10. The use of the exterior material for lithium ion batteries according to any one of claims 1 to 8, wherein: the method comprises the steps of heating and curing an outer packaging material for a lithium ion battery, forming a concave part by deep drawing or bulging, accommodating a battery body in the concave part, folding back the remaining part without the concave part, and performing heat sealing under the condition that a lug extending from a battery positive electrode and a battery negative electrode is clamped at the edge part, wherein the heat sealing is performed at the temperature of 150-230 ℃ and under the pressure of 0.1-1 MPa for 1-30 s.
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