CN110643177B - High-strength lithium battery packaging film and preparation method thereof - Google Patents

High-strength lithium battery packaging film and preparation method thereof Download PDF

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CN110643177B
CN110643177B CN201910972206.3A CN201910972206A CN110643177B CN 110643177 B CN110643177 B CN 110643177B CN 201910972206 A CN201910972206 A CN 201910972206A CN 110643177 B CN110643177 B CN 110643177B
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packaging film
layer
nylon
aluminum foil
heat sealing
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CN110643177A (en
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邵峥
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Ningbo Ruicheng Packing Material Co ltd
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Ningbo Ruicheng Packing Material Co ltd
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B15/14—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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/51—Elastic
    • 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
    • B32B2307/554—Wear resistance
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    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The invention discloses a high-strength lithium battery packaging film and a preparation method thereof, wherein the high-strength lithium battery packaging film comprises a nylon layer, an aluminum foil layer and a heat sealing layer, wherein the nylon layer consists of MXD6, nylon 6, glass fiber, LLDPE-g-MAH, a silane coupling agent, an antioxidant, a flame retardant, nano silicon dioxide, hydroquinone and aluminum ions; the heat sealing layer is composed of polypropylene, carbon fiber, nano calcium carbonate, talcum powder and barium sulfate. The high-strength lithium battery packaging film prepared by the invention changes the raw materials of the nylon layer and the heat sealing layer, and improves the service performance.

Description

High-strength lithium battery packaging film and preparation method thereof
Technical Field
The invention relates to the technical field of lithium battery packaging films, in particular to a high-strength lithium battery packaging film and a preparation method thereof.
Background
The lithium battery packaging film in the prior art generally comprises a nylon layer, an aluminum foil layer and a heat sealing layer, and a dry process or a thermal process can be adopted for preparing the lithium battery packaging film during preparation, the performance of the lithium battery packaging film is closely related to the service life of a lithium battery, and how to improve the strength, toughness and other properties of the lithium battery packaging film by changing the performances of the nylon layer and the heat sealing layer under the condition that the performance of the aluminum foil layer is not changed is the direction to be researched by workers in the field.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to: provided is a high-strength lithium battery packaging film.
In order to solve the problems, the technical solution of the invention is as follows: the high-strength lithium battery packaging film comprises a nylon layer, an aluminum foil layer and a heat sealing layer;
the nylon layer is composed of the following raw materials in percentage by mass: MXD 642%, nylon 615%, glass fiber 30%, LLDPE-g-MAH 9%, silane coupling agent 0.2%, antioxidant 0.3%, flame retardant 0.1%, nano-silica 3%, hydroquinone 0.2%, and the balance of aluminum ions;
the heat sealing layer is composed of the following raw materials in percentage by mass: 70% of polypropylene, 28% of carbon fiber, 1% of nano calcium carbonate, 0.5% of talcum powder and 0.5% of barium sulfate.
Further, the thickness of the heat sealing layer is 60-65 microns.
The invention also provides a preparation method of the high-strength lithium battery packaging film, which comprises the following steps:
(1) mixing polypropylene, carbon fiber, nano calcium carbonate, talcum powder and barium sulfate, and preparing a heat sealing layer after molding through a co-extrusion casting machine;
(2) degreasing and corrosion-resisting the surface of the aluminum foil to prepare an aluminum foil layer;
(3) injecting aluminum ions into MXD6 by using an ion injector, mixing MXD6, nylon 6, glass fiber, LLDPE-g-MAH, silane coupling agent, antioxidant, flame retardant, nano silicon dioxide and hydroquinone, extruding and molding by using an extruder after mixing, and preparing a nylon layer by biaxial stretching;
(4) compounding and molding the nylon layer, the aluminum foil layer and the heat sealing layer by a dry process;
(5) and (3) carrying out performance test on the prepared packaging film, wherein the performance test comprises the following steps:
(51) bonding two packaging films with a tab, taking a seal with a certain width, cutting the seal into strips, testing the peel strength by using a tensile testing device, and observing whether the aluminum foil layer of the peeled packaging film is uniform milky white or not, wherein the aluminum foil layer and the aluminum foil layer are required to be not layered;
(52) the packaging film is deeply punched by a good forming die, the forming depth is adjusted within a certain value range until the edge angle of the packaging film is cracked, and the maximum depth value before cracking is recorded;
(53) sealing and welding two sides of the formed packaging film, not adding a lug and a battery cell, injecting a certain amount of electrolyte, baking for a certain time at a certain temperature, observing, and observing whether the packaging film is corroded, leaked, expanded and layered after sealing and welding;
(54) placing the packaging film in a water bath or a high-temperature high-humidity environment, taking out after a period of time, observing whether the packaging film is abnormal, judging the water absorption capacity of the packaging film through weighing or moisture test, and testing the barrier property of the packaging film;
(6) and packaging the qualified product after the test.
The invention has the beneficial effects that:
the glass fiber is used as a reinforcing material, so that the strength of the nylon layer can be improved, when the content of the glass fiber is 30%, the notch impact strength can reach the maximum value, and the tensile strength is higher; the MXD6 has good interface compatibility with the silicon dioxide nanoparticles, so that the tensile strength and the notch impact strength of the MXD 6/nano silicon dioxide composite material are improved to different degrees compared with those of pure MXD6, and an elastic transition layer is formed between the nylon matrix and the silicon dioxide nanoparticles along with the addition of the nano silicon dioxide, so that the stress on the interface can be effectively transmitted and relaxed, the external impact energy can be better absorbed and dispersed, and the toughness of the material is improved; the antioxidant is used for keeping the thermal oxidation stability of the nylon layer; hydroquinone is used as an anti-aging agent and can inhibit the action of external factors such as light, heat, oxygen and the like; the aluminum ions are injected into MXD6 through an ion injection method, the hydrogen ions in MXD6 macromolecular chain amido bonds are replaced by the aluminum ions, and the aluminum ions are uniformly injected into a molecular intercalation layer or a macromolecular chain, the surface hardness of MXD6 can be greatly improved, the wear resistance of MXD6 is greatly improved, and the elastic modulus is also improved;
the carbon fiber is added into the polypropylene to improve the strength of the polypropylene, the nano calcium carbonate is used as a nucleating agent, the crystallization speed, the crystallization rate and the crystallization fineness ratio of the polypropylene can be improved, so that the rigidity of the polypropylene is increased, and the talcum powder and the barium sulfate are used as fillers to obviously improve the rigidity, the heat resistance, the dimensional stability, the high-temperature creep resistance, the hardness and the like of the polypropylene.
Drawings
FIG. 1 is a graph of Glass Fiber (GF) content versus MXD6 tensile strength;
fig. 2 is a graph of Glass Fiber (GF) content versus MXD6 notched impact strength.
Detailed Description
For a more intuitive and complete understanding of the technical solution of the present invention, non-limiting features are described as follows:
the first embodiment is as follows:
the high-strength lithium battery packaging film comprises a nylon layer, wherein the nylon layer is composed of the following raw materials in percentage by mass: MXD 642%, nylon 615%, glass fiber 30%, LLDPE-g-MAH 9%, silane coupling agent 0.2%, antioxidant 0.3%, flame retardant 0.1%, nano-silica 3%, hydroquinone 0.2%, and the balance of aluminum ions; an aluminum foil layer; the heat sealing layer is composed of the following raw materials in percentage by mass: 70% of polypropylene, 28% of carbon fiber, 1% of nano calcium carbonate, 0.5% of talcum powder and 0.5% of barium sulfate.
The preparation method of the high-strength lithium battery packaging film comprises the following steps:
(1) mixing polypropylene, carbon fiber, nano calcium carbonate, talcum powder and barium sulfate, and preparing a heat sealing layer after molding through a co-extrusion casting machine;
(2) degreasing and corrosion-resisting the surface of the aluminum foil to prepare an aluminum foil layer;
(3) injecting aluminum ions into MXD6 by using an ion injector, mixing MXD6, nylon 6, glass fiber, LLDPE-g-MAH, silane coupling agent, antioxidant, flame retardant, nano silicon dioxide and hydroquinone, extruding and molding by using an extruder after mixing, and preparing a nylon layer by biaxial stretching;
(4) compounding and molding the nylon layer, the aluminum foil layer and the heat sealing layer by a dry process;
(5) and (3) carrying out performance test on the prepared packaging film, wherein the performance test comprises the following steps:
(51) bonding two packaging films with a tab, taking a seal with a certain width, cutting the seal into strips, testing the peel strength by using a tensile testing device, and observing whether the aluminum foil layer of the peeled packaging film is uniform milky white or not, wherein the aluminum foil layer and the aluminum foil layer are required to be not layered;
(52) the packaging film is deeply punched by a good forming die, the forming depth is adjusted within a certain value range until the corner of the packaging film breaks, the maximum depth value before the breaking is recorded, and the following conditions must be met after the packaging film is deeply punched: the thinnest parts of the four corners of the punched pit are not less than 50% of the original thickness, the thickness of the heat sealing layer is 60-65 micrometers, otherwise, leakage points exist after the battery is formed, and the performance of the battery is seriously influenced;
(53) sealing and welding two sides of the formed packaging film, not adding a lug and a battery cell, injecting a certain amount of electrolyte, baking for a certain time at a certain temperature, observing, and observing whether the packaging film is corroded, leaked, expanded and layered after sealing and welding;
(54) placing the packaging film in a water bath or a high-temperature high-humidity environment, taking out after a period of time, observing whether the packaging film is abnormal, judging the water absorption capacity of the packaging film through weighing or moisture test, and testing the barrier property of the packaging film;
(6) and packaging the qualified product after the test.
As shown in fig. 1 and 2, the glass fiber is used as a reinforcing material to improve the strength of the nylon layer, and when the content of the glass fiber is 30%, the notch impact strength can reach the maximum value, and the tensile strength is also higher.
The MXD6 has good interface compatibility with the silicon dioxide nanoparticles, so that the tensile strength and the notch impact strength of the MXD 6/nano silicon dioxide composite material are improved to different degrees compared with those of pure MXD6, and an elastic transition layer is formed between the nylon matrix and the silicon dioxide nanoparticles along with the addition of the nano silicon dioxide, so that the stress on the interface can be effectively transmitted and relaxed, the external impact energy can be better absorbed and dispersed, and the toughness of the material is improved.
The antioxidant is used for keeping the thermal oxidation stability of the nylon layer.
Hydroquinone is used as an anti-aging agent to inhibit the action of external factors such as light, heat, oxygen, etc.
The MXD6 is injected by the ion injection method, the hydrogen ions in MXD6 macromolecular chain amido bonds are replaced by the aluminum ions, and the aluminum ions are uniformly injected into the molecular intercalation or the macromolecular chains, the MXD6 surface hardness can be greatly improved, the MXD6 wear resistance is greatly improved, and the elastic modulus is also improved.
The carbon fiber is added into the polypropylene to improve the strength of the polypropylene, the nano calcium carbonate is used as a nucleating agent, the crystallization speed, the crystallization rate and the crystallization fineness ratio of the polypropylene can be improved, so that the rigidity of the polypropylene is increased, and the talcum powder and the barium sulfate are used as fillers to obviously improve the rigidity, the heat resistance, the dimensional stability, the high-temperature creep resistance, the hardness and the like of the polypropylene.

Claims (2)

1. High strength lithium cell packaging film, including nylon layer, aluminium foil layer and heat-seal layer, its characterized in that:
the nylon layer is composed of the following raw materials in percentage by mass: MXD 642%, nylon 615%, glass fiber 30%, LLDPE-g-MAH 9%, silane coupling agent 0.2%, antioxidant 0.3%, flame retardant 0.1%, nano-silica 3%, hydroquinone 0.2%, and the balance of aluminum ions;
the heat sealing layer is composed of the following raw materials in percentage by mass: 70% of polypropylene, 28% of carbon fiber, 1% of nano calcium carbonate, 0.5% of talcum powder and 0.5% of barium sulfate;
the preparation method comprises the following steps:
(1) mixing polypropylene, carbon fiber, nano calcium carbonate, talcum powder and barium sulfate, and preparing a heat sealing layer after molding through a co-extrusion casting machine;
(2) degreasing and corrosion-resisting the surface of the aluminum foil to prepare an aluminum foil layer;
(3) injecting aluminum ions into MXD6 by using an ion injector, mixing MXD6, nylon 6, glass fiber, LLDPE-g-MAH, silane coupling agent, antioxidant, flame retardant, nano silicon dioxide and hydroquinone, extruding and molding by using an extruder after mixing, and preparing a nylon layer by biaxial stretching;
(4) compounding and molding the nylon layer, the aluminum foil layer and the heat sealing layer by a dry process;
(5) and (3) carrying out performance test on the prepared packaging film, wherein the performance test comprises the following steps:
(51) bonding two packaging films with a tab, taking a seal, cutting the seal into strips, testing the peeling strength by using a tensile testing device, and observing whether the aluminum foil layer of the peeled packaging film is uniform milky white or not, wherein the aluminum foil layer and the aluminum foil layer are required to be not layered;
(52) the packaging film is deeply punched by a good forming die, the forming depth is adjusted until the edge of the packaging film breaks, and the maximum depth before the breaking is recorded;
(53) sealing and welding two sides of the formed packaging film, injecting electrolyte without adding a lug and a battery core, baking, observing, and observing whether the packaging film is corroded, leaked, expanded and layered after sealing and welding;
(54) placing the packaging film in a water bath or a high-temperature high-humidity environment, taking out the packaging film to observe whether the packaging film is abnormal or not, judging the water absorption capacity of the packaging film through weighing or moisture test, and testing the barrier property of the packaging film;
(6) and packaging the qualified product after the test.
2. The high-strength lithium battery packaging film according to claim 1, wherein: the thickness of the heat sealing layer is 60-65 microns.
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CN114335827B (en) * 2021-12-20 2024-04-02 广东广麟材耀新能源材料有限公司 Anti-cracking aluminum plastic film

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