CN115851157A - Electrolyte corrosion-resistant outer packaging material for lithium ion battery device - Google Patents

Electrolyte corrosion-resistant outer packaging material for lithium ion battery device Download PDF

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CN115851157A
CN115851157A CN202211488919.0A CN202211488919A CN115851157A CN 115851157 A CN115851157 A CN 115851157A CN 202211488919 A CN202211488919 A CN 202211488919A CN 115851157 A CN115851157 A CN 115851157A
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layer
corrosion
resin
intermediate metal
resin layer
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庄志
王卉
程跃
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Jiangsu Ruijie New Material Technology Co ltd
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Jiangsu Ruijie New Material Technology Co ltd
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Abstract

The invention discloses an electrolyte corrosion resistant outer packaging material for a lithium ion battery device, which comprises an outer base material resin layer, an intermediate metal layer, an inner layer adhesive layer and a hot welding resin layer; the outer base material resin layer is arranged on the middle metal layer, the middle metal layer is arranged on the inner layer adhesive layer, and the inner layer adhesive layer is arranged on the hot-melt resin layer; wherein the intermediate metal layer is subjected to a corrosion-resistant treatment to form a corrosion-resistant layer. Through corrosion-resistant treatment of the middle metal layer, the defects that the existing metal-plastic composite film is poor in corrosion resistance and low in peeling force between the metal layer and the hot-melt resin layer are overcome, and meanwhile corrosion resistance performance and electrolyte peeling strength of the metal-plastic composite film are improved.

Description

Electrolyte corrosion-resistant outer packaging material for lithium ion battery device
Technical Field
The invention relates to the technical field related to lithium ion batteries, in particular to an external packaging material for a lithium battery electrolyte corrosion resistant device.
Background
At present, lithium ion batteries are mainly divided into three types, namely square, cylindrical and soft package, wherein the square and cylindrical shells mainly adopt hard shells made of aluminum alloy, stainless steel and the like, the aluminum alloy shells can be made of aluminum materials, and the soft package shell formed by stacking metal and resin adopts a metal-plastic composite film, so that the problem of inflexible appearance design of hard-package batteries is greatly improved.
The metal-plastic composite film comprises an outer base material resin layer, an outer adhesive layer, an intermediate metal layer, an inner adhesive layer and a hot-melt resin layer in sequence from outside to inside. As a battery outer packaging material, the metal-plastic composite film is required to have electrolyte corrosion resistance, so that the problems of liquid leakage and the like of a battery shell can be prevented, and the service life of the battery is ensured.
Generally, metals in the metal-plastic composite film for lithium ion battery outer packaging are subjected to corrosion prevention treatment, and when water is mixed in the battery manufacturing process, the metals react with lithium salt in the electrolyte to generate corrosive Hydrogen Fluoride (HF) when the corrosion prevention treatment effect is not good, and the hydrogen fluoride passes through the thermal welding resin layer and the inner layer adhesive layer to reach the surface of the intermediate metal layer, so that the metals are corroded, and the metals and the thermal welding resin layer are separated. The possibility of occurrence of leakage of the electrolyte from the battery is increased. Therefore, the metal corrosion-resistant treatment has a great influence on the metal-plastic composite film.
At present, the main components of the corrosion prevention treatment solution of the metal-plastic composite film are trivalent chromium compounds, fluorides, aminated phenol resin and phosphoric acid. After the metal is subjected to the anti-corrosion treatment by the anti-corrosion liquid, the corrosion resistance degree of the metal-plastic composite film can be improved in some common electrolyte environments. However, in the long-term use of the battery, moisture may permeate through the battery outer package to generate Hydrogen Fluoride (HF) in the electrolyte, and the corrosion prevention treatment effect of the corrosion prevention solution is not ideal, so that the interlayer separation of the metal-plastic composite film for the lithium ion battery is easily caused, and the popularization and the use of the metal-plastic composite film in the field of the lithium ion battery are influenced.
Disclosure of Invention
In view of the above, the present invention is to provide a metal-plastic composite film, which solves the problems of the existing metal-plastic composite film, such as poor corrosion resistance and low peeling force between the metal layer and the thermal welding resin layer, and improves the corrosion resistance and the electrolyte peeling strength of the metal-plastic composite film.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the invention provides an electrolyte corrosion resistant outer packaging material for a lithium ion battery device, which is characterized in that: the anti-corrosion coating comprises an intermediate metal layer and an anti-corrosion layer formed by the intermediate metal layer through corrosion resistance treatment.
Is characterized in that the adhesive further comprises an outer base resin layer, an inner adhesive layer and a hot-melt resin layer; the outer base material resin layer is arranged on the middle metal layer, the middle metal layer is arranged on the inner layer adhesive layer, and the inner layer adhesive layer is arranged on the hot-melt resin layer; wherein the corrosion protection layer is disposed between the intermediate metal layer and the inner adhesive layer.
Is characterized by further comprising an outer-layer adhesive layer, wherein the outer-layer base material resin layer is arranged on the outer-layer adhesive layer which is arranged on the middle metal layer; wherein the intermediate metal layer is disposed between the outer adhesive layer and the inner adhesive layer.
Is characterized in that the metal of the middle metal layer is a nickel-plated steel plate, and the thickness of a nickel-plated layer of the nickel-plated steel plate is 0.5-20 μm.
Characterized in that the carbon component and the metal component of the anti-corrosion layer are distributed in a gradient manner.
Characterized in that the element components on the anti-corrosion layer on the side of the heat welding resin layer are distributed in a gradient manner, the content ratio of carbon (C) on the outermost layer of the anti-corrosion layer on the side of the heat welding resin layer is more than or equal to 40% and less than or equal to 100%, the content ratio of nickel (Ni) is less than or equal to 10%, and the content ratio of fluorine (F) is less than or equal to 10%; in the layer 40nm below the surface layer of the anti-corrosion layer, the content of carbon (C) is less than or equal to 10%, the content of nickel (Ni) is more than or equal to 30% and less than or equal to 100%, and the content of fluorine (F) is less than or equal to 20%.
Characterized in that after the liquid-resistant treatment, the proportion of the content of carbon (C) is less than or equal to 10%, the proportion of the content of nickel (Ni) is greater than or equal to 30%, and the proportion of the content of fluorine element (F) is less than or equal to 25% in the layer which is 40nm below the most surface layer of the anti-corrosion layer on the side of the heat welding resin layer.
Characterized in that the anti-corrosion layer is formed by drying an anti-corrosion liquid, wherein the anti-corrosion liquid mainly comprises a trivalent chromium compound, an inorganic acid, an organic resin, a bridging agent and a solvent consisting of water or an organic solvent or a mixed solution thereof.
Characterized in that the bridging agent contains at least one of an amino resin, a melamine resin, a phenol resin, an epoxy compound, a blocked isocyanate compound, an oxazoline compound, a carbodiimide compound, a condensate of formaldehyde and an alkyl-mono-alcohol having 1 to 4 carbon atoms, a condensate of carbolic acid and formaldehyde, and a derivative thereof.
Characterized in that the trivalent chromium compound and the bridging agent in the anti-corrosion liquid used for forming the anti-corrosion layer at least comprise one of chromium nitrate and chromium fluoride: the corrosion preventing solution for forming the corrosion preventing layer contains titanium (Ti) compound or zirconium (Zr) compound in the content of 0-0.6% and 0-2.8%, respectively.
The invention has the following beneficial effects:
1) The invention provides an electrolyte corrosion resistant outer packaging material for a lithium ion battery device, which overcomes the defects of poor corrosion resistance and low peeling force between a metal layer and a thermal welding resin layer of the existing metal-plastic composite film by performing corrosion resistant treatment on an intermediate metal layer, and improves the corrosion resistance performance and the electrolyte peeling strength of the metal-plastic composite film;
2) The invention provides a method for preparing an anti-corrosion layer by treating and drying an intermediate metal layer with an anti-corrosion liquid, which obviously improves the corrosion resistance of an outer packaging material for a lithium ion battery device and shows excellent corrosion resistance by the configuration of the anti-corrosion layer;
3) The present invention provides a highly corrosion-resistant battery, which contains the outer packaging material for a corrosion-resistant battery device, thereby reducing the poor corrosion resistance of the battery device, improving the defect of low peeling force between a metal layer and a heat-sealing resin layer, and showing excellent corrosion resistance;
4) The invention firstly proposes that the intermediate metal layer is made of nickel-plated steel plate material, elements in the surface anti-corrosion layer are distributed in a gradient manner, and the initial peeling strength between the intermediate metal layer and the hot-melt adhesive resin layer of the metal-plastic composite film and the corrosion resistance in the electrolyte environment with more water addition can be improved by controlling the carbon (C) content of the outermost layer and the intermediate metal element and fluorine (F) element content at the inner layer (40 nm) in the anti-corrosion layer.
Drawings
Fig. 1 shows the structure of an outer package for a lithium ion battery device resistant to electrolyte corrosion according to the present invention.
Description of component reference numerals
1 \ 8230and outer base material resin layer
2' \ 8230and intermediate metal layer
3 8230and inner adhesive layer
4-8230and hot-melt resin layer
5 8230a layer of outer adhesive
6' \ 8230and anti-corrosion layer
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Embodiments of the present invention provide a highly corrosion-resistant outer package material for a battery device and a battery.
The invention provides an electrolyte corrosion resistant outer packaging material (also called metal-plastic composite film) for a lithium ion battery device, which mainly comprises an outer base material resin layer 1, an intermediate metal layer 2, an inner layer adhesive layer 3 and a hot welding resin layer 4; the outer base material resin layer 1 is arranged on the middle metal layer 2, the middle metal layer 2 is arranged on the inner layer adhesive layer 3, and the inner layer adhesive layer 3 is arranged on the hot-melt resin layer 4; wherein the anti-corrosion layer 6 formed by the corrosion-resistant treatment of the intermediate metal layer 2 is arranged between the intermediate metal layer 2 and the inner-layer adhesive layer 3.
Specifically, the adhesive comprises an outer adhesive layer 5, wherein the outer base material resin layer 1 is arranged on the outer adhesive layer 5, the outer adhesive layer 5 is arranged on the middle metal layer 2, and the middle metal layer 2 is arranged between the outer adhesive layer 5 and the inner adhesive layer 3.
Specifically, the metal of the intermediate metal layer 2 is a nickel-plated steel plate.
Specifically, the nickel-plated layer of the nickel-plated steel sheet has a thickness of 0.5 μm to 20 μm.
Specifically, the intermediate metal layer 2 is subjected to corrosion-resistant treatment at least on the side of the thermal fusion resin layer 4 to form the corrosion-resistant layer 6, and the special corrosion-resistant liquid for the corrosion-resistant treatment mainly contains a trivalent chromium compound, an inorganic acid, an organic resin, a bridging agent, and a solvent composed of water or an organic solvent, or a mixture thereof. Wherein, the proportion of the solvent composed of the trivalent chromium compound, the inorganic acid, the organic resin, the water or the organic solvent or the mixed solution thereof is 1.9 to 6 percent, 0.3 to 6 percent, 0.6 to 6 percent and 78.6 to 97.2 percent respectively. The bridging agent is contained in an amount of 0.01 to 30% by mass based on the solid content of the corrosion-resistant layer 6, or 0.05 to 15% by mass based on the solid content of the solution for forming the corrosion-resistant layer 6.
And drying the anti-corrosion liquid to form the anti-corrosion layer 6, wherein the element components on the middle metal anti-corrosion layer on the side of the heat welding resin layer 4 are distributed in a gradient manner, the content ratio of carbon (C) on the outermost layer of the anti-corrosion layer 6 on the side of the heat welding resin layer 4 is more than or equal to 40%, the content ratio of nickel (Ni) is less than or equal to 10%, and the content ratio of fluorine (F) is less than or equal to 10%. In the 40nm layer from the surface layer of the anti-corrosion layer 6, the content ratio of carbon (C) is less than or equal to 10%, the content ratio of nickel (Ni) is greater than or equal to 30%, and the content ratio of fluorine (F) is less than or equal to 20%.
Specifically, the intermediate metal layer 2 on which the corrosion-preventing layer 6 was formed was compounded with the heat-fusible resin layer 4 with an internal adhesive, and then the resultant was subjected to an electrolyte (containing 1mol/L LiPF) containing 1000PPM of water 6 The mixed solvent of EC, DEC and DMC, wherein the mass ratio of EC to DEC to DMC is 1.
Specifically, the trivalent chromium compound and the bridging agent in the corrosion preventing solution used for forming the corrosion preventing layer 6 are at least one of chromium nitrate and chromium fluoride.
Specifically, the trivalent chromium compound is preferably at least one of chromium nitrate and chromium fluoride. The trivalent chromium compound has the function of increasing the crosslinking degree of the anticorrosive film on the surface of the intermediate metal.
Specifically, the bridging agent contains at least one of an amino resin, a melamine resin, a phenol resin, an epoxy compound, a blocked isocyanate compound, an oxazoline compound, a carbodiimide compound, a condensate of formaldehyde and an alkyl monool having 1 to 4 carbon atoms, a condensate of carbolic acid and formaldehyde, and a derivative thereof.
Specifically, the bridging agent contains at least one of silicon compounds such as silicon dioxide, zirconium compounds such as zirconium ammonium fluoride and zirconium ammonium carbonate, metal chelates such as titanium chelates, and inorganic bridging substances of metal salts such as Ca, al, mg, fe, zn.
Specifically, the corrosion preventing liquid used for forming the corrosion preventing layer 6 contains a titanium (Ti) compound or a zirconium (Zr) compound in an amount of 0 to 0.6% and 0 to 2.8%, respectively.
Specifically, the inorganic acid in the corrosion preventing liquid used for forming the corrosion preventing layer 6 is at least one of phosphoric acid, nitric acid and hydrofluoric acid; the organic resin is at least one of acrylic resin, methacrylic resin, hydroxy acrylic resin, polyvinyl alcohol resin and phenolic resin; the Ti compound at least comprises one of titanium fluoride and titanium nitrate, and the Zr compound at least comprises one of zirconium fluoride and zirconium nitrate; the organic solvent is at least one of isopropanol, ethanol and ethylene glycol monobutyl ether.
Specifically, the organic resin is composed of at least one of acrylic resin, methacrylic resin, hydroxyacrylic resin, polyvinyl alcohol resin, olefin resin, and phenol resin; the organic resin plays a role in improving the film forming property of the anti-corrosion layer on the surface of the intermediate metal and bonding with the inner adhesive layer 3;
specifically, the inorganic acid is at least one of phosphoric acid, nitric acid and hydrofluoric acid, and the inorganic acid plays a role in removing an oxide film on the surface of the intermediate metal;
specifically, a titanium (Ti) compound or a zirconium (Zr) compound is taken as a secondary central crosslinking point to play a role in enhancing the corrosion resistance of the surface of the intermediate metal;
specifically, the organic solvent at least comprises one of isopropanol, ethanol and ethylene glycol monobutyl ether, and the organic solvent is used for reducing the surface tension of the anti-corrosion liquid and increasing the leveling property of the anti-corrosion liquid on the surface of the intermediate metal;
specifically, if the content of the intermediate metal element in the surface layer of the corrosion-resistant layer 6 in which the elements are distributed in a gradient manner is 10% or more, it is found that the hydrofluoric acid resistance effect is not good when the thickness of the corrosion-resistant layer 6 is too small.
Specifically, if the content of fluorine element (F) in the layer 40nm below the surface layer of the corrosion prevention layer 6 after the electrolyte resistance is 25% or more, the effect of suppressing the corrosion by hydrogen fluoride generated from the electrolyte is low. In the composite film, the peel strength between the inner layer adhesive layer 3 and the intermediate metal layer 2 may be significantly reduced during long-term storage.
The present invention provides a highly corrosion-resistant battery, specifically, an exterior material for a corrosion-resistant battery device, which comprises all of the above-described materials.
The corrosion protection layer 6 of the outer packaging material is characterized as follows:
the anti-corrosion layer is used in the packing material of lithium ion battery to avoid the hydrogen fluoride produced by the reaction of electrolyte and water to corrode the surface of the intermediate metal layer, prevent the separation between the intermediate metal layer and the hot melt resin layer, maintain the homogeneity of the surface of the intermediate metal layer, reduce the change of the adhesion (wettability) and prevent the delamination between the intermediate metal layer and the hot melt resin layer in the metal-plastic composite film. Preferably, the corrosion-preventing layer is formed by applying the corrosion-preventing liquid to at least the surface of the intermediate metal layer opposite to the outer base resin side, and preferably, the corrosion-preventing layer is formed on both sides of the intermediate metal layer. The anti-corrosion layer is formed on the surface of the intermediate metal layer in contact with the outer base material resin layer, so that the surface uniformity of the intermediate metal layer is stable, the change of the cohesiveness (wettability) is reduced, the composite film can be stored for a long time in a high-temperature and high-humidity environment, and the anti-delamination effect is achieved between the outer base material resin layer and the intermediate metal layer of the metal-plastic composite film.
In this patent, the corrosion prevention layer is characterized in that the carbon component from the corrosion prevention layer and the metal component from the intermediate metal layer are distributed in a gradient slope between the heat-fusion resin layer and the intermediate metal layer. That is, since the carbon component from the corrosion prevention layer on the heat-welding resin layer side increases the carbon component of the heat-welding resin layer in contact with the corrosion prevention layer, the stability of the composition of the heat-welding resin layer and the intermediate metal can be ensured. If the adhesiveness of the inner layer adhesive layer is unstable, the adhesion is lowered and the peel strength is unstable when the electrolyte penetrates. In addition, the intermediate metal content in the corrosion protection layer measured increases with depth, indicating an increase in adhesion of the corrosion protection layer to the intermediate metal layer. When the lithium battery with the flexible package is used for a long time, the invaded moisture reacts with the electrolyte to generate hydrogen fluoride, the dissolution of the anti-corrosion layer on the middle metal layer is inhibited, and the long-term stability of the peeling strength of the inner-layer adhesive layer and the middle metal layer is ensured. And the effect increases with increasing fluoride content in the corrosion protection layer. This is presumably because the fluoride component increases the hydrogen fluoride blocking property.
Further, since the components of the corrosion-preventing layer exhibit a gradient distribution in a gradient, it is presumed that the effective components in the corrosion-preventing solution are reaction products between the resin components that generate the corrosion-preventing layer on the heat-welded resin layer side, for example, reaction products of the resin in the corrosion-preventing layer and chromium (Cr), reaction products of titanium (Ti), zirconium (Zr), reaction products of an inorganic acid and chromium (Cr), and reaction products of a fluoride or an inorganic acid in the intermediate metal layer and the corrosion-preventing layer.
In this patent, the corrosion-resistant layer is formed by further limiting the drying of the corrosion-resistant liquid, and the carbon (C) content ratio of the outermost layer of the corrosion-resistant layer on the side of the heat-welded resin layer is 40% or more and 100% or less, the nickel (Ni) content ratio is 10% or less, and the fluorine (F) content ratio is 10% or less. In the layer 40nm below the surface layer of the anti-corrosion layer, the content of carbon (C) is less than or equal to 10%, the content of nickel (Ni) is more than or equal to 30% and less than or equal to 100%, and the content of fluorine (F) is less than or equal to 20%. If the ratio of the carbon (C) content in the top layer of the anti-corrosion layer on the heat-welded resin layer side is less than 40% or the content of the metal element in the middle furnace is greater than 10%, as described above, the adhesion strength between the anti-corrosion layer and the inner layer adhesive layer is unstable, and the peel strength is reduced during the storage process due to the influence of the electrolyte. Or the content of the metal element is increased, resulting in a decrease in the internal insulation property. The reduction in internal insulation causes problems such as a reduction in the life of the battery, and leakage of the electrolyte due to an electrical short circuit between the outer material and the inside of the battery.
On the basis of the above, the method is further limited to compounding the intermediate metal layer for forming the anti-corrosion layer with the thermal welding resin layer by using an internal adhesive, and adding 1000PPM of electrolyte (containing 1mol/L LiPF) 6 The mixed solvent of EC, DEC and DMC, wherein the mass ratio of EC to DEC to DMC is 1The content of carbon (C) in the layer which is 40nm below the outermost layer of the side anti-corrosion layer is less than or equal to 10%, the content of nickel (Ni) is greater than or equal to 30%, and the content of fluorine element (F) is less than or equal to 25%. If the fluorine element (F) content exceeds 25% in the 40nm layer from the surface layer to the lower layer, the reaction product between the corrosion-preventing layer and the intermediate metal layer is reduced, and the peel strength between the inner layer adhesive layer and the intermediate metal layer may be significantly reduced during long-term storage. As described above, the corrosion-preventing layer formed by the reaction of the resin, acid, chromium, and the intermediate metal element forming the corrosion-preventing layer has a large carbon (C) content on the heat-fusion bonding layer side, but has a composition gradient structure in which the amount of the intermediate metal element increases as the temperature approaches the intermediate metal layer side, whereby the penetration of hydrogen fluoride, which can corrode the intermediate metal, can be suppressed even when the electrolytic solution is contacted and the electrolytic solution penetrates or the electrolytic solution reacts with water while maintaining the adhesion to the heat-fusion bonding layer. Further, in order to suppress permeation of hydrogen fluoride and the electrolytic solution, the inclined structure is a cross-linked structure. Important factors for the formation of the crosslinked structure are the combination of the corrosion prevention layer and the intermediate metal layer and the heat treatment process in which the crosslinking reaction occurs. It is particularly noted that in the case where the heat treatment conditions are inappropriate, sufficient battery content suitability cannot be obtained. The ratio of the fluorine element (F) to the intermediate metal layer element is a ratio of a content of the fluorine element (F) detected when a content of an element derived from the intermediate metal layer detected by a method (XPS-ESCA method) described later is 1.
In this patent, the element or component of the intermediate metal layer refers to an element of the intermediate metal layer, and an element of the intermediate metal layer detected from a product formed by a reaction between a constituent material of the corrosion-resistant layer, an electrolyte solution, or the like and the intermediate metal layer. When the intermediate metal layer is a nickel-plated steel sheet, it is a component derived from nickel, but it may contain other alloying components added thereto.
When the elements are measured by the method described later, the elements detected in this patent include components derived from the intermediate metal layer, as well as constituent elements of the corrosion-preventing layer and the electrolytic solution. For example, carbon (C), oxygen (O), nitrogen (N), chromium (Cr), phosphorus (P), silicon (Si), fluorine (F), titanium (Ti), zirconium (Zr), cerium (Ce), and the like.
A trace amount of metal element may be added to the material forming the corrosion prevention layer. In the measurement, when the metal element is not distinguishable from the element derived from the intermediate metal layer, the entire metal element may be measured as the metal element derived from the intermediate metal layer, or the metal element added to the corrosion prevention layer may be subtracted from the detected amount of the metal element, assuming that the metal element added to the corrosion prevention layer is uniformly dispersed in the corrosion prevention layer.
When the corrosion prevention layer is a multilayer, the judgment can be made by a single layer in contact with the intermediate metal layer, or by the whole multilayer portion.
As an example of the corrosion prevention layer, the corrosion prevention layer of the present invention may mainly include a thin film obtained by a coating type corrosion prevention treatment containing at least one component selected from an oxide sol of a rare earth element, an anionic polymer, and a cationic polymer. The coating agent may contain phosphoric acid, phosphate, and a crosslinking agent for crosslinking the polymer. In the rare earth element oxide sol, fine particles of a rare earth element oxide (for example, particles having an average particle diameter of 100nm or less) are dispersed in a liquid dispersion medium. The rare earth element oxide mainly contains cerium oxide, yttrium oxide, neodymium oxide, lanthanum oxide, and the like, and cerium oxide is preferable from the viewpoint of further improving the adhesion. The rare earth element oxide contained in the corrosion prevention layer may be used alone or in combination of two or more. As the liquid dispersion medium of the rare earth element oxide sol, various solvents such as water, an alcohol-based solvent, a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, and an ether-based solvent can be used, and water is preferred. The cationic polymer mainly includes polyethylene pipe imine, a complex ion polymer complex formed by a polymer containing polyethylene pipe imine and carboxylic acid, a primary amine grav-torr acrylic resin obtained by graft copolymerization of primary amine on an acrylic main chain, polyacetic acid or its derivative, aminated phenol, and the like. Further, as the anionic polymer, a copolymer mainly containing poly (meth) acrylic acid or a salt thereof, or (meth) acrylic acid or a salt thereof is preferable. The crosslinking agent is preferably at least 1 of a compound having any one of an isocyanate chemical group, a glycidyl chemical group, a carboxyl chemical group, and an oxazoline chemical group, and a silane coupling agent.
More specifically, the corrosion protection solution of the present invention is an aqueous solution mainly composed of a trivalent chromium compound, an inorganic acid, an organic resin, a bridging agent, a titanium (Ti) compound or a zirconium (Zr) compound, and an organic solvent, wherein the proportions of the trivalent chromium compound, the inorganic acid, the organic resin, the titanium (Ti) compound or the zirconium (Zr) compound, the organic solvent, and water are 1.9 to 6%, 0.3 to 6%, 0.6 to 6%, 0 to 0.6%, 0 to 2.8%, and 78.6 to 97.2%, respectively. The bridging agent is 0.01-30% by mass of the solid content of the anti-corrosion layer, or 0.05-15% by mass of the solid content of the solution for forming the anti-corrosion layer.
The trivalent chromium compound and the bridging agent at least consist of one of chromium nitrate and chromium fluoride; the inorganic acid is at least one of phosphoric acid, nitric acid and hydrofluoric acid; the organic resin is at least one of acrylic resin, methacrylic resin, hydroxy acrylic resin, polyvinyl alcohol resin, olefin resin and phenolic resin; the titanium (Ti) compound is at least one of titanium fluoride and titanium nitrate; the zirconium (Zr) compound is composed of one of zirconium fluoride and zirconium nitrate; the organic solvent is at least one of isopropanol, ethanol and ethylene glycol monobutyl ether.
The addition of the bridging agent can increase the crosslinking density of the corrosion-resistant layer, thereby stabilizing the resistance of the corrosion-resistant layer to the electrolyte as the content and hydrogen fluoride generated by the reaction of the electrolyte with water. More preferably, a bridging agent may be added to the corrosion preventing solution for forming the corrosion preventing layer.
The crosslinking agent may be an organic crosslinking agent or an inorganic crosslinking agent. The inorganic bridging agent includes at least one of silicon compounds such as silicon dioxide, zirconium compounds such as zirconium ammonium fluoride and zirconium ammonium carbonate, metal chelates such as titanium chelates, and inorganic bridging substances of metal salts such as Ca, al, mg, fe, zn. The organic bridging agent may preferably be at least one of an amino resin, a melamine resin, a phenol resin, an epoxy compound, a blocked isocyanate compound, an oxazoline compound, a carbodiimide compound, a condensate of formaldehyde and a monohydric alkyl alcohol having 1 to 4 carbon atoms, a condensate of carbolic acid and formaldehyde, and a derivative of the above.
The bridging agent is contained in the corrosion-resistant layer at 0.01 to 30% by mass in terms of solid content of the corrosion-resistant layer, or at 0.05 to 15% by mass in terms of solid content of the solution for forming the corrosion-resistant layer. When the content of the bridging agent is less than 0.05%, the degree of improving the corrosion resistance by adding the bridging agent is very low. If the content exceeds 15%, the crosslinking density of the corrosion-resistant layer increases, the corrosion-resistant layer becomes too hard, and cracking and peeling of the corrosion-resistant layer are likely to occur during the molding process, resulting in a decrease in corrosion resistance.
In addition, as an anticorrosive layer formed by chemical conversion treatment, various anticorrosive solutions mainly containing phosphates, nitric acid, chromates, fluorides, rare earth oxides, and the like are known.
The chemical conversion treatment using a phosphate or a chromate mainly includes, for example, chromium chromate treatment, chromium phosphate treatment, phosphoric acid-chromate treatment, and the like, and examples of chromium compounds used in these treatments include chromium nitrate, chromium fluoride, chromium sulfate, chromium acetate, chromium oxalate, chromium biphosphate, chromium acetate, chromium chloride, and chromium sulfate. The chromate treatment method mainly includes etching chromate treatment, electrolytic chromate treatment, coating chromate treatment, and the like, but coating chromate treatment is preferable. In the coating chromate treatment, a treatment liquid containing a metal phosphate such as a chromium phosphate (Cr) salt, a titanium phosphate (Ti) salt, a zirconium phosphate (Zr) salt, or a lead (Zn) phosphite and a mixture of these metal salts as a main component, or a treatment liquid containing a nonmetal phosphate and a mixture of these nonmetal salts as a main component is mixed with a synthetic resin and then applied to the degreased surface by a known coating method such as a roll coating method, a gravure printing method, or an immersion method, followed by drying. Various solvents such as water, alcohol solvents, hydrocarbon solvents, ketone solvents, ester compound solvents, and ether solvents can be used as the treatment liquid, but water is preferred. As the resin component used in this case, a water-soluble polymer such as an aminated phenol or a polyacrylic acid-based resin can be selected.
An example of the corrosion-preventing layer is formed by applying a particulate material in which a metal oxide such as alumina, titanium oxide, cerium oxide, or tin oxide and precipitated barium sulfate are dispersed in phosphoric acid to the surface of the intermediate metal layer and then performing a sintering treatment at 150 ℃.
As a method of applying the corrosion preventing liquid, at least the internal thermal adhesive resin layer of the intermediate metal layer is degreased by a treatment method such as an alkali immersion method, an electrolytic cleaning method, an acid cleaning method, an electrolytic acid cleaning method, an oxygen activation method, or a heat treatment (annealing treatment) for calendering. Then, the anti-corrosion liquid of the invention is applied by a bar coating method, a roll coating method, a gravure coating method, a dipping method and the like, and a high-temperature chemical combination reaction is performed on the surface of the intermediate metal layer, and the amount of the coating wet film of the anti-corrosion liquid on the intermediate metal layer is in the range of 1.6 to 3.2g/m 2 And after the anti-corrosion liquid is coated, performing heat treatment at the high temperature of 130-200 ℃ for 0.5-5 min to form the anti-corrosion layer.
The thickness of the corrosion-preventing layer is not particularly limited, but is preferably 1nm to 3.0 μm, more preferably 1nm to 1.5 μm, from the viewpoint of the adhesion force between the intermediate metal layer and the hot-melt resin layer.
The trivalent chromium compound and the bridging agent in the corrosion preventing liquid for forming the corrosion preventing treatment layer are preferably one of chromium nitrate and chromium fluoride. The chromium nitrate and chromium fluoride react with the resin, the intermediate metal layer and the inorganic acid in the anti-corrosion layer, and the chromium fluoride can improve the hydrogen fluoride resistance of the anti-corrosion layer and ensure the stability of the peeling strength of the inner layer thermal welding resin layer and the intermediate metal layer during long-term storage.
The titanium (Ti) compound or zirconium (Zr) compound can improve the stability and uniformity of the reaction of chromium with resin, metal, inorganic acid. The titanium (Ti) compound is preferably titanium fluoride or titanium nitrate. The zirconium (Zr) compound is preferably zirconium fluoride or zirconium nitrate.
The inorganic acid can remove the surface oxide film of the intermediate metal layer, so that the metal can quickly react with the components in the anti-corrosion layer to form a firm chromium reaction product. Therefore, the peel strength stability of the heat-fusion resin layer and the intermediate metal layer can be ensured when the composite film is stored for a long time. As the inorganic acid, one of phosphoric acid, nitric acid, and hydrofluoric acid is preferable.
As described above, the organic resin can improve the adhesion stability of the intermediate metal layer and the inner adhesive layer. In addition, in the corrosion prevention layer, since the reaction product of chromium (Cr), titanium (Ti), and zirconium (Zr) has resistance to the electrolyte and hydrogen fluoride generated from the electrolyte, the peel strength stability of the heat-sealing resin layer and the intermediate metal layer can be improved. The organic resin preferably contains one of an acrylic resin, a methacrylic resin, a hydroxyacrylic resin, a polyvinyl alcohol resin, an olefin resin, and a phenol resin.
The organic solvent may be used alone as a solvent or may be added to water. The wettability of the corrosion-resistant liquid can be improved, and the reaction stability of the corrosion-resistant layer and the intermediate metal layer can be improved. In addition, the surface tension of the anticorrosive solution can be reduced, and the uniformity of the coating film can be improved. The organic solvent may be one selected from isopropyl alcohol, ethanol, and ethylene glycol butyl ether.
The outer base resin layer 1 of the outer packaging material is characterized as follows:
in the present invention, the outer base resin layer is provided to function as a base material of a packaging material for a lithium ion battery. The outer base resin layer is positioned on the outer layer side of the packaging material for the lithium ion battery.
The material for forming the outer base resin layer is not particularly limited as long as it has at least an insulating property as a function of the base.
There are various methods for preparing the outer substrate resin layer. For example, a resin film product may be formed directly from a resin, or a coated resin product may be formed. The resin film may be an unstretched film or an stretched film. The stretched film may be a uniaxially stretched film or a biaxially stretched film, and a biaxially stretched film is preferable. As a method for producing the biaxially stretched film, for example, a stepwise biaxial stretching method, a blown film method, a simultaneous stretching method are exemplified. Examples of the resin coating method include a roll coating method, a gravure coating method, and an extrusion coating method.
Examples of the resin forming the outer base resin layer include resins such as polyester, polyamide, polyolefin, epoxy resin, acrylic resin, fluororesin, polyurethane, silicone resin, and phenol resin, and modified products of these resins. The resin forming the outer base resin layer may be a copolymer of these resins, a modified product of the copolymer, or a mixture of these resins.
Preferably a single layer or a plurality of layers
As the resin forming the outer base resin layer, polyester and polyamide are preferably listed.
Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and copolyester. Examples of the copolyester include a copolyester mainly composed of ethylene terephthalate as a repeating unit. Specifically, a copolymer polyester obtained by polymerizing ethylene terephthalate as a main repeating unit and ethylene isophthalate (hereinafter, simply referred to as a copolyester (terephthalate/isophthalate)), a copolyester (terephthalate/adipate), a copolyester (terephthalate/sodium isophthalate), a copolyester (terephthalate/phenyl-dicarboxylate), a copolyester (terephthalate/decanedicarboxylate), or the like. These polyesters may be used alone in 1 kind, or 2 or more kinds may be used in combination.
Specific examples of the polyamide include aliphatic polyamides such as nylon 6, nylon 66, nylon 610, nylon 12, nylon 46, and copolymers of nylon 6 and nylon 66; a hexamethylenediamine-isophthalic acid-terephthalic acid copolymer polyamide such as nylon 6I, nylon 6T, nylon 6IT, and nylon 6I6T (I represents isophthalic acid, and T represents terephthalic acid) containing a terephthalic acid-and/or isophthalic acid-derived structural unit, and an aromatic polyamide such as polyamide MXD6 (polyamide PACM6 (poly bis (4-aminocyclohexyl) methane azide)), and these polyamides may be used alone in 1 kind or in combination of 2 or more kinds.
The outer base resin layer preferably contains at least one of a polyester film, a polyamide film, and a polyolefin film; preferably at least one of a stretched polyester film, a stretched polyamide film and a stretched polyolefin film; further preferably comprises at least one of a stretched polyethylene terephthalate film, a stretched polybutylene terephthalate film, a stretched nylon film, and a stretched polypropylene film; further preferably, the film comprises at least one of a biaxially oriented polyethylene terephthalate film, a biaxially oriented polybutylene terephthalate film, a biaxially oriented nylon film, and a biaxially oriented polypropylene film.
The outer base resin layer may be a single layer or may be composed of 2 or more layers. When the outer base resin layer is composed of 2 or more layers, the outer base resin layer may be a composite film formed by the action of an adhesive, or may be a resin composite film formed by co-extruding resins into 2 or more layers. Further, a resin composite film formed by coextruding resins into 2 or more layers may be used as the outer base resin layer in an unstretched state, or may be uniaxially or biaxially stretched to be used as the outer base resin layer.
Specific examples of the laminate of 2 or more resin films in the outer base resin layer include a composite film of a polyester film and a nylon film, a2 or more nylon composite film, and a2 or more polyester composite film. Preferred are a laminate of a stretched nylon film and a stretched polyester film, a stretched nylon composite film having 2 or more layers, and a stretched polyester composite film having 2 or more layers. For example, when the outer base resin layer is a 2-layer resin composite film, a composite film of a polyester resin film and a polyester resin film, a composite film of a polyamide resin film and a polyamide resin film, or a composite film of a polyester resin film and a polyamide resin film is preferable, and a composite film of a polyethylene terephthalate film and a polyethylene terephthalate film, a composite film of a polybutylene terephthalate film and a polybutylene terephthalate film, a composite film of a nylon film and a nylon film, or a composite film of a polyethylene terephthalate film and a nylon film is more preferable. In addition, since the polyester resin is less likely to be discolored when the electrolyte solution adheres to the surface, when the outer base resin layer is a resin composite film having two or more layers, the polyester resin film is preferably located on the outermost layer of the outer base resin layer.
When the outer base resin layer is a resin composite film having two or more layers, the two or more layers may be combined with an adhesive. As a preferable adhesive, a glue solution having the same composition as the outer layer adhesive can be used. The method for laminating two or more resin films is not particularly limited, and a dry lamination method, a sandwich lamination method, an extrusion lamination method, a thermal lamination method, or the like can be used, and a dry lamination method is preferred. When the composite is carried out by a dry composite method, a reactive polyurethane adhesive is preferably used as the reactive adhesive of the outer layer. At this time, the thickness of the adhesive layer may be about 2 to 5 μm. When the outer base resin layer is formed by a resin coating method, the outer base resin layer may be formed by first dissolving the resin in an organic solvent and then coating the solution. As the coating resin, a phenol resin such as a polyamide resin, a polyimide resin, a polyurethane resin, an epoxy resin, an acrylic resin, a polyester resin, a polyamide resin, a polyimide resin, a fluorine-based copolymerized resin, and a polyester resin, and an amino resin such as a polyester resin, a polycarbonate resin, a urea resin, and a melamine resin can be used.
Further, one or more additives such as a lubricant, a flame retardant, an anti-blocking agent, an antioxidant, a light stabilizer, a tackifier, and an antistatic agent may be added to the surface and the inside of the outer base resin layer.
From the viewpoint of improving the moldability of the packaging material for lithium ion batteries, it is preferable to form a lubricant on the surface of the outer base resin layer. The lubricant is not particularly limited, but an amide-based lubricant is preferable. The amide-based lubricant includes saturated fatty acid amides, unsaturated fatty acid amides, substituted amides, methylol amides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, fatty acid amides, aromatic bisamides, and the like. As the saturated fatty acid amide, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, and the like can be used, for example. Examples of the unsaturated fatty acid amide include oleamide and erucamide. Substituted amides include N-oil palmitamide, N-stearamide, N-oil stearamide, and N-stearamide. In addition, the methylolamide includes methylolstearic acid amide and the like. The saturated fatty acid bisamide includes methylenebisstearamide, ethylenebisoctanoamide, ethylenebislaurate amide, ethylenebisstearamide, ethylenebishydroxystearamide, ethylenebisbehenamide and hexamethylenebisstearamide, n '-distearyladipamide, n' -distearylsebacate amide and the like. Unsaturated fatty acid bisamides include ethylene bisoleic acid amide, ethylene biserucamide, hexamethylene bisoleic acid amide, n '-dioleyl adipic acid amide, and n, n' -dioleyl sebacic acid amide. Fatty acid ester amides include stearamide ethyl stearate and the like. The aromatic bisamide includes m-xylylene bisstearamide, m-xylylene bishydroxystearamide, n' -distearyl isophthalic acid amide, and the like. The lubricant may be used alone in 1 kind, or two or more kinds may be used in combination.
When the lubricant is present on the surface of the outer base resin layer, the amount of application is not particularly limited, but it is preferably about 3mg/m 2 Above, more preferably from 4 to 30mg/m 2 Left and right.
The lubricant present on the surface of the outer base resin layer may be a lubricant that has oozed out from the base resin layer containing the lubricant, or a lubricant that has been applied to the surface of the outer base resin layer.
The thickness of the outer base resin layer is not particularly limited as long as it functions as a base. When the outer base resin layer is a resin composite film having 2 or more layers, the thickness of the resin film constituting each layer is preferably about 2 to 30 μm.
In the invention, the outer base resin layer can be a single-layer or more than two-layer composite film formed by one or more of polymer materials such as blown film nylon, synchronous or asynchronous biaxially oriented polyethylene terephthalate (PET), synchronous or asynchronous biaxially oriented polybutylene terephthalate (PBT), polyimide (PI) and the like, the outer base resin can be bonded to the middle metal layer in one or a combination of coextrusion, coating, compounding and hot sticking, and the total thickness of the outer base resin layer is 5-35 mu m. When the thickness is less than 5 μm, moldability and insulation properties are relatively poor. When the thickness exceeds 35. Mu.m, the total thickness of the metal-plastic composite film becomes too large, and the flexibility, which is an advantage of the metal-plastic composite film, is deteriorated.
The outer adhesive layer 5 of the outer packaging material is characterized in that:
in the packaging material for a lithium ion battery of the present invention, when the outer base resin layer and the intermediate metal layer are combined, whether or not to provide the outer adhesive layer may be determined as necessary. The outer adhesive layer is formed for the purpose of improving the adhesion between the outer base resin layer and the intermediate metal layer.
The outer adhesive layer is formed of an adhesive capable of bonding the outer base resin layer and the intermediate metal layer. The adhesive used for forming the outer adhesive layer is not limited, and may be, for example, a two-component curing adhesive (two-component adhesive) or a one-component curing adhesive (one-component adhesive). The adhesive used for forming the outer adhesive layer may be any of a chemical reaction type, a solvent volatilization type, a hot melt type, a hot press type, and the like. The outer adhesive layer may be a single layer or a plurality of layers.
The outer adhesive layer is a two-component polyurethane adhesive formed by using polyester polyol, polyurethane modified polyol and the like as diol main agents and aromatic or aliphatic isocyanate as a curing agent. The curing agent may be selected according to the functional group of the adhesive component, and may be appropriately selected from a polyfunctional epoxy resin, a methanesulfonic acid-containing polymer, a porlyamine resin, an inorganic acid, and the like. Examples of the main agent for the outer adhesive layer include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and copolyester; a polyether resin; a polyurethane resin; an epoxy resin; a phenolic resin; polyamide resins such as nylon 6, nylon 66, nylon 12, and copolyamide; polyolefin resins such as polyolefin, cyclic polyolefin, acid-modified polyolefin, and acid-modified cyclic polyolefin; polyvinyl acetate; cellulose; (meth) acrylic resins; a polyimide resin; a polycarbonate; amino resins such as urea resins and melamine resins; rubbers such as chloroprene rubber, nitrile rubber, and styrene-butadiene rubber; silicone resins, and the like. These adhesive components can be used alone in 1, also can be used in 2 or more combinations.
The combination of the outer adhesive layer more preferred in the present invention is one or two of binary or polybasic polyester, polyurethane modified polyester and isocyanate. The isocyanate is not particularly specified in the compounds having two or more isocyanate groups in the molecule. For example, one or a mixture of two or more of polymers such as isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), diphenylmethane 4,4' -diisocyanate (MDI), and hexamethylene 1, 6-diisocyanate (HDI).
The outer layer adhesive layer may contain a colorant, a thermoplastic elastomer, a tackifier, a filler, and the like, as long as the addition of other components is not inhibited. The outer adhesive layer contains a coloring agent, whereby the packaging material for lithium ion batteries can be colored. As the colorant, a colorant such as a pigment or a dye can be used. Further, 1 kind of the colorant may be used, or two or more kinds may be mixed and used.
The type of the pigment is not particularly limited as long as the adhesiveness of the outer layer adhesive layer is not impaired. Examples of the organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, thioindigo pigments, perylene pigments, isoindoline pigments, and the like; as the inorganic pigment, carbon black-based, titanium oxide-based, cadmium-based, lead-based, isoindoline-based pigments and the like can be used.
Among the coloring agents, carbon black is preferable, for example, in order to make the appearance of the packaging material for lithium ion batteries black.
The average particle diameter of the pigment is not particularly limited, and may be selected from about 0.05 to 5 μm, preferably about 0.08 to 2 μm. The average particle diameter of the pigment is a median diameter measured by a laser diffraction/scattering particle size distribution measuring apparatus.
The content of the pigment in the outer layer adhesive layer is not particularly limited as long as the packaging material for lithium ion batteries is colored, and is preferably about 5 to 60%, more preferably 10 to 40%.
The thickness of the outer layer adhesive layer is not particularly limited as long as the outer base resin layer 1 and the intermediate metal layer 3 can be bonded to each other, and a preferable range is about 1 to 10 μm, and more preferably about 2 to 5 μm.
The colored layer is a layer provided between the outer base resin layer and the intermediate metal layer as necessary. The colored metal-plastic composite film can be formed directly by adding a pigment to the outer adhesive layer, and a colored layer can also be formed between the outer base resin layer and the outer adhesive layer. Further, the colored layer may be provided outside the outer base resin layer.
The colored layer can be formed by, for example, applying ink containing a colorant to the surface of the outer base resin layer 1, the surface of the outer adhesive layer a, or the surface of the intermediate metal layer. As the colorant, a colorant such as a pigment or a dye can be used. In addition, only 1 kind of colorant may be used, or 2 or more kinds may be mixed and used.
As a specific example of the coloring agent contained in the colored layer, the example described with reference to the outer layer adhesive layer can be cited.
The intermediate metal layer 2 of the outer package material is characterized as follows:
in the outer package material for a lithium ion battery, the intermediate metal layer is a barrier layer capable of at least suppressing the entry of moisture.
In this patent, a nickel-plated steel sheet is used as a metal material used for the intermediate metal layer.
When the middle metal layer is a nickel-plated steel plate, the nickel-plated layer has the anti-corrosion effects such as rust prevention and the like, and also has the effect of improving the surface cleanliness. By forming an anti-corrosion layer described later on the surface of the nickel plating, the anti-corrosion property of the nickel plating and the synergistic effect with the anti-corrosion layer significantly improve the electrolyte resistance. The thickness of the nickel plating layer may be 20 μm or less. Preferably 1 to 5 μm. When the thickness exceeds 20 μm, the corrosion resistance is improved, but cracks are likely to be generated by external pressure load such as molding.
In addition, the surface cleanliness of the intermediate metal layer greatly affects the corrosion prevention effect, and therefore, it is important to manage the surface cleanliness of the intermediate metal layer. Surface cleanliness can be managed by a method using a wetting agent test for wettability or a method using a contact angle as an index. The index of wettability is D or higher, preferably B. Further, the contact angle is 25 ° or less, preferably 20 ° or less, and more preferably 15 ° or less, when measured with pure water as an index of the contact angle. When the wettability is lower than D or the contact angle exceeds 25 °, the reactivity with an anti-corrosion layer described later and the initial adhesion are deteriorated. If the reactivity deteriorates and the reaction between the corrosion-preventing layer and the intermediate metal layer becomes insufficient, the resistance to permeation of the electrolyte solution as a battery content and the resistance to hydrogen fluoride generated in the reaction between the electrolyte and water decrease. As time passes, the adhesion of the corrosion-resistant layer to the intermediate metal layer decreases, the corrosion-resistant layer dissolves, and the intermediate metal layer and the corrosion-resistant layer may peel off, thereby shortening the life of the battery. The same applies to the case where the initial adhesion between the corrosion-resistant layer and the intermediate metal layer is deteriorated.
The method for testing the surface wettability of the metal layer in Zhongzhou area can use "national standard of the people's republic of China GB/T225638.5-2016, methods for testing metals, part 5: detection of wettability ". The contact angle test method in Zhongyuan can employ "national standard of the people's republic of China GB/T22638.9-2008, method for testing metals section 9: measurement of hydrophilicity ".
The inner layer adhesive layer 3 of the outer packaging material is characterized as follows:
in the packaging material for a lithium ion battery of the present invention, the inner layer adhesive layer is an intermediate layer provided to firmly bond the intermediate metal layer and the heat-fusible resin layer.
The inner layer adhesive layer is formed of a resin capable of bonding the intermediate metal layer and the heat-fusible resin layer. The heat-sealing resin layer may be formed of polyolefin, cyclic polyolefin, or modified polyolefin resins such as carboxylic acid-modified polyolefin, carboxylic acid-modified cyclic polyolefin, methacrylic acid-modified polyolefin, acrylic acid-modified polyolefin, crotonic acid-modified polyolefin, and imide-modified polyolefin. From the viewpoint of improving the adhesion between the intermediate metal layer and the heat-fusible resin layer, the modified polyolefin is preferably a modified polyolefin resin such as acrylic acid, methacrylic acid, maleic acid, anhydrous maleic anhydride, or polyamide. The resin constituting the inner adhesive layer may or may not contain a polyolefin main chain, preferably a polyolefin main chain. Whether or not the resin constituting the inner adhesive layer contains a polyolefin main chain can be analyzed by, for example, infrared spectroscopy, gas chromatography-mass spectrometry, or the like, and the analysis method is not particularly limited. The polyolefin and its modified resin used in the inner layer adhesive are the same as those used in the heat-fusible resin layer, and are polypropylene resins or copolymers of propylene and ethylene.
The inner layer adhesive layer may be a resin composition containing an acid-modified polyolefin and a curing agent, from the viewpoint of stability of the packaging material for lithium ion batteries in long-term use. The acid-modified polyolefin is particularly preferably a maleic anhydride-or acrylic acid-modified polyolefin.
The curing agent is not particularly limited as long as it is a curing agent for curing the acid-modified polyolefin. Curing agents such as epoxy curing agents, polyfunctional isocyanate curing agents, carbodiimide curing agents, and oxazoline curing agents can be used.
The epoxy curing agent is not particularly limited as long as it is a compound having at least 1 epoxy group. For example, epoxy resins such as bisphenol a diglycidyl ether, modified bisphenol a diglycidyl ether, novolac glycidyl ether, glycerol polyglycidyl ether, and polyglycerol polyglycidyl ether are used.
The polyfunctional isocyanate curing agent is not particularly limited as long as it is a compound having 2 or more isocyanate groups in the molecule. For example, isophorone diisocyanate (PDI), hexamethylene Diisocyanate (HDI), toluene Diisocyanate (TDI), polymerized or added components of diphenylmethane diisocyanate (MDI) or mixtures of these with other polymers.
The carbodiimide-based curing agent is not particularly limited as long as it is a compound having at least 1 carbodiimide group (-N = C = N-) in the molecule. Polycarbodiimide compounds having at least 2 or more carbodiimide groups are preferred.
The oxazoline-based curing agent is not particularly limited as long as it is a compound having an oxazoline skeleton.
The curing agent may be composed of two or more compounds from the viewpoint of improving the adhesion between the inner layer adhesive layer and the heat-sealing resin layer.
The thickness of the inner layer adhesive layer is not particularly limited as long as it functions as an adhesive layer, and is preferably about 1 to 80 μm, and more preferably about 1 to 50 μm.
The main components of the inner layer adhesive layer are a single layer or more than two layers of film layers formed by a mixture of 1 or more than 2 of modified polyolefin resin, block copolymerization polypropylene resin (B-PP) with the content of polypropylene (PP) more than 50%, random copolymerization polypropylene resin (R-PP) and homopolymerization polypropylene resin (H-PP).
The inner layer adhesive layer may be formed by a solution type inner layer adhesive layer method or a hot melt type inner layer adhesive resin layer method when the intermediate metal layer and the hot melt resin layer are laminated.
The solution type inner layer adhesive layer is prepared by dissolving an acid-modified polyolefin resin as a main solvent and 1 or 2 or more kinds of isocyanate, epoxy resin or oxazoline or amine compounds such as triethylamine, N-dimethylethanolamine as a curing agent in at least 1 or 2 or more kinds of solvents such as water, ethanol, isopropanol, ethyl acetate, methyl ethyl ketone, toluene, methylcyclohexane and the like, uniformly coating the solution on the surface of the metal subjected to the corrosion protection treatment, and heating to volatilize the solvent so that the thickness of the inner layer adhesive layer can achieve the desired effect, preferably about 1 to 10 μm, more preferably 1 to 5 μm. When the thickness is less than 1 μm, the thickness becomes thin, and the adhesion between the intermediate metal layer and the heat-fusible resin layer is lowered, which causes a problem in adhesion. When the thickness exceeds 10 μm, there is no problem in adhesion, but when the curing agent is reacted, a hard resin layer is formed, the bending resistance is deteriorated, the flexibility of the metal-plastic composite film is lowered, there is a risk of cracking due to bending, and the intermediate metal layer and the heat-sealing resin layer may be peeled off. The melting point of the acid-modified polyolefin resin in the solution type inner layer adhesive is 60 to 155 ℃, the weight average molecular weight is in the range of 10000 to 150000, and the acid value of the solution type inner layer adhesive is in the range of 0.5 to 200 mgKOH/g. The solution type inner layer adhesive is mainly composed of an acid-modified polyolefin and an amine compound as a hardener in a ratio of 10:1, preferably 15. The acid used for modifying the polyolefin is maleic acid, fumaric acid, methacrylic acid, or the like, and the amine compound is at least one of triethylamine or N, N-2 methylethanolamine. The acid modified polyolefin is polypropylene with melting point above 110 ℃, and the content of polypropylene is above 50%.
If the melting point is 60 ℃ or lower, the heat resistance is low, and the intermediate metal layer and the heat-fusible resin layer may peel off at high temperature. When the temperature exceeds 155 ℃, the heat resistance is good, but when the temperature is reacted with a curing agent, a hard resin layer is formed, and the flexibility of the metal-plastic composite film is deteriorated, or cracks are generated by bending, and the intermediate metal layer and the heat-sealing resin layer may be peeled off. When the weight average molecular weight is 10000 or less, the fluidity of the resin is high during heating, the thickness becomes extremely thin during heat sealing, the adhesion strength between the intermediate metal layer and the heat-sealable resin layer (in the case of a reaction in which a curing agent is added) becomes low, and there is a problem in sealability. If the weight average molecular weight exceeds 150000, the intermediate metal layer and the heat-fusible resin layer (in the case of reaction with the addition of a curing agent) form a hard resin layer, and the bending resistance is deteriorated, so that the flexibility of the metal-plastic composite film is lowered, or cracks are generated by bending, and the intermediate metal layer and the heat-fusible resin layer may be peeled off. If the acid value of the acid-modified polyolefin resin is less than 0.5mgKOH/g, the curing reaction points with the curing agent are small, and the adhesion between the intermediate metal layer and the heat-sealable resin layer is unstable. If the acid value exceeds 200mgKOH/g, the curing reaction between the curing agent and the acid-modified polyolefin resin is too severe, and a hard resin layer is formed, whereby the bending resistance is deteriorated, the flexibility of the metal-plastic composite film is lowered, or cracks are generated by bending, and the intermediate metal layer and the heat-sealing resin layer may be peeled off.
The inner layer adhesive layer used for the intermediate metal layer and the heat-fusion resin layer is a heat-fusion type inner layer adhesive, and the resin used for the heat-fusion type inner layer adhesive layer is an acid-modified polyolefin resin having a melting point of 135 to 165 ℃ and an MFR (230 ℃) of 3 to 15g/10 min. The thickness of the inner layer adhesive layer formed is 2 to 80 μm, preferably 5 to 50 μm. The acid-modified polyolefin resin used for the hot-melt type inner layer adhesive has a degree of modification of 1% to 15%, preferably 3% to 12%. When the melting point of the acid-modified polyolefin resin is 135 ℃ or lower, the resin fluidity increases by heating, and when heat-sealed under pressure, the thickness becomes too thin, and the adhesion strength between the intermediate metal layer and the heat-sealing resin layer becomes low, which causes a problem of sealing properties. When the melting point is 165 ℃ or higher, the fluidity is relatively low at the time of pressure heat sealing and the heat resistance is improved, but when the heat-shrinkable film is compounded with the intermediate metal layer, the heat shrinkage increases, so that the internal stress increases and the adhesion of the heat-fusible inner layer adhesive to the intermediate metal layer is lowered. Therefore, if the film is stored for a long period of time, the film may be peeled off from the intermediate metal layer. Further, heat shrinkage occurs due to heating at the time of heat sealing, and the adhesion between the intermediate metal layer and the intermediate metal layer is reduced, whereby the sealing strength is lowered, and the sealing property is a serious problem. When the MFR (230 ℃) of the acid-modified polyolefin resin is less than 3g/10min, the extrusion film-forming property tends to be unstable when the resin is extruded onto the intermediate metal layer after heat-melting and compounded. If the MFR (230 ℃) of the acid-modified polyolefin resin is higher than 15g/10min, the resin fluidity increases by heating, the thickness becomes too thin at the time of heat sealing under pressure, the adhesion strength between the intermediate metal layer and the heat-sealable resin layer becomes low, and there is a problem in sealability. When the thickness of the hot-melt type inner layer adhesive layer is less than 2 μm, heat shrinkage cannot be absorbed because of an excessive amount of heat shrinkage when it is compounded with the intermediate metal layer. Therefore, the bonding force with the intermediate metal layer is reduced due to the increase of the internal stress. If the film is stored for a long period of time, the film may be peeled off from the intermediate metal layer. When the thickness of the hot-melt type inner layer adhesive layer exceeds 80 μm, physical problems do not occur, but the production price is increased, and therefore, it is preferable to avoid the use thereof. When the modification degree of the hot-melt type inner layer adhesive layer is less than 1%, the adhesiveness with the intermediate metal layer is unstable. If the degree of modification exceeds 15%, the physical properties will not be problematic, but the production cost will increase, and therefore it is preferable to avoid such a phenomenon.
The heat-fusion resin layer 4 of the exterior material is characterized as follows:
in the exterior material for a lithium ion battery of the present invention, the heat-sealable resin layer corresponds to the innermost layer, and is a layer (heat-seal layer) that functions to seal the battery element by heat-fusing the heat-sealable resin layers to each other when the battery is assembled.
The resin constituting the heat-fusible resin layer is not particularly limited, but is preferably a resin having a polyolefin main chain, such as polyolefin and acid-modified polyolefin.
Specific examples of the polyolefin include polyethylene ethylene- α -olefin copolymers such as low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene; polypropylene such as homopolypropylene, polypropylene block copolymer (for example, a block copolymer of propylene and ethylene), and polypropylene random copolymer (for example, a random copolymer of propylene and ethylene); propylene- α -olefin copolymers; ethylene-butene-propylene terpolymers, and the like. Among them, polypropylene is preferable. The polyolefin resin in the case of the copolymer may be a block copolymer or a random copolymer. These polyolefin-based resins may be used alone in 1 kind, or may be used in 2 or more kinds.
The acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization with a polyolefin using an acid component. As the acid-modified polyolefin, a copolymer obtained by copolymerizing the above polyolefin with a polar molecule such as polyacrylic acid or methacrylic acid, or the like, may be used. As the acid component used for acid modification, carboxylic acids or sulfonic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, and anhydrides thereof can be used, and acrylic acid, maleic acid, and anhydrides thereof are preferably used.
The heat-sealing resin layer may be composed of 1 resin alone, or may be composed of a combination of 2 or more resins. The heat-sealing resin layer may have only 1 layer, or may be composed of 2 or more layers of the same or different resins.
The heat-sealing resin layer may contain a slipping agent or the like as required. When the heat-sealing resin layer contains a slipping agent, the moldability of the outer packaging material for lithium ion batteries can be improved. The type of the slipping agent is not particularly limited and may be selected from known ranges. The slipping agent can be used alone 1 kind, or more than 2 kinds can be used in combination.
The lubricant is not particularly limited, but an amide-based lubricant is preferably used. The slipping agent can be used alone 1 kind, or more than 2 kinds can be used in combination. The amide-based slip agent is preferably used on the surface of the outer base resin layer.
When a slipping agent is present on the surface of the heat-fusible resin layer, the content thereof is not particularly limited, but is preferably 10 to 50mg/m from the viewpoint of improving moldability of the electronic packaging material 2 Further preferably 15 to 40mg/m 2 。
The slipping agent present on the surface of the heat-fusion resin layer may be one which bleeds out from the resin constituting the heat-fusion resin layer, or one which is applied to the surface of the heat-fusion resin layer.
The thickness of the heat-fusible resin layer is not particularly limited as long as it satisfies the function of sealing the battery element after the heat-fusible resin layers are heat-fused to each other, and may be about 100 μm or less, more preferably about 25 to 80 μm.
The heat-sealing resin layer may contain an antioxidant or the like as necessary. The heat-sealing resin layer containing an antioxidant can suppress thermal deterioration in the production process. The kind of the antioxidant is not particularly limited, and may be selected from known ranges. The antioxidant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The heat welding resin in the invention is a single layer or a composite layer consisting of 1 or a mixture of more than 2 of acid modified polyolefin resin, homopolymerized polypropylene resin, block copolymerization polypropylene resin, random copolymerization polypropylene resin and polyethylene resin.
The resin used for the heat-fusible resin layer is a single layer or a composite layer composed of a mixture of 1 or more than 2 of those having a melting point of 120 to 162 ℃, preferably 130 to 162 ℃, and an MFR (230 ℃) of 2 to 15g/10min, more preferably an MFR (230 ℃) of 3 to 12g/10min, and has a thickness of 20 to 120 μm, more preferably 25 to 80 μm. When the inner weld resin layer is a composite layer, the thickness of the resin on the reverse side in contact with the intermediate metal layer is 2 μm or more, and the melting point is 130 to 152 ℃. When the melting point is 120 ℃ or lower, the fluidity is high when heated, and when heat-sealed under pressure, the thickness becomes thin, and the adhesion to the intermediate metal layer is reduced. In addition, the resin flows to the non-pressed edge part by pressing, the expansion and contraction of the battery and the external force of bending process cause cracks, the electrolyte penetrates to the middle metal layer through the cracks, the insulation resistance of the thermal welding resin layer is reduced, the electric leakage phenomenon occurs, and the service life of the battery is shortened. When the melting point exceeds 162 ℃, the crystallinity of the resin increases, so that the fluidity at the time of heat sealing under pressure becomes relatively low, and the heat resistance increases. Therefore, when the battery is subjected to external force such as expansion and contraction and bending, the resin layer is likely to crack, and stable sealing properties over a long period of time cannot be obtained. When the MFR (230 ℃) of the resin is less than 2g/10min, the fluidity of the resin at the time of heat-sealing under pressure is low, and it is difficult to obtain stable sealability. When the MFR (230 ℃) of the resin exceeds 15g/10min, the resin fluidity is too high at the time of heat sealing under pressure, the resin thickness becomes seriously thin, and the sealing property is hardly stabilized. In addition, the resin flows to the non-pressed edge part by pressing, the expansion and contraction of the battery and the external force of bending process cause cracks, the electrolyte penetrates to the middle metal layer through the cracks, the insulation resistance of the thermal welding resin layer is reduced, the electric leakage phenomenon occurs, and the service life of the battery is shortened. When the thickness of the heat-sealing resin layer is less than 20 μm, the thickness cannot sufficiently cover variations in the machining dimensions and variations in conditions of a heat-sealing device or the like, and therefore it is difficult to obtain a uniform heat-sealed portion, and stable sealing properties cannot be obtained. In addition, the resin flows to the non-pressed edge part by pressing, the thickness of the thermal welding resin layer becomes thin, the expansion and contraction of the battery and the external force of bending processing are easy to cause cracks, the electrolyte penetrates to the middle metal layer through the cracks, the insulation resistance of the thermal welding resin layer is reduced, the electric leakage phenomenon is caused, and the service life of the battery is shortened. When the thickness of the thermal welding resin layer exceeds 120 μm, the water vapor permeation amount increases, the water content in the battery increases, gas is generated by reaction with the electrolyte, the danger of expansion, rupture, and leakage easily occurs, the battery life decreases, and the excessive hydrogen fluoride corrodes the metal layer subjected to the corrosion prevention treatment, which causes a decrease in the adhesion strength between the intermediate metal layer and the thermal welding resin layer, and the problem of electrolyte leakage easily occurs.
The compounding process of the metal-plastic composite film comprises the following steps:
1. and (3) deoiling the intermediate metal layer, wherein the surface wettability of the intermediate metal layer is 65dyn/cm, preferably 70dyn/cm or more, or the titration contact angle of distilled water is 15 degrees or less, preferably 10 degrees or less. If the wettability or surface water contact angle of the intermediate metal layer exceeds a given range, it indicates that the possibility of rolling oil remaining on the metal in the production stage is high, so that the adhesion capability of the interface formed between the intermediate metal layer and the thermal welding resin layer becomes poor, and the intermediate metal layer and the thermal welding resin layer are likely to fall off during long-term storage of the battery, and the battery leakage is likely to occur, and as a preventive measure, the annealing treatment at a temperature of 150 ℃ or more may be performed, or the degreasing treatment by plasma, corona method or alkali solution may be performed, and the alkali degreasing method is to dip the metal in the alkali solution at a temperature of 50 to 65 ℃, wash the metal with deionized water for 2 times after a certain period of treatment, and then dry the metal to obtain the degreased metal
2. Forming an anti-corrosion layer on the intermediate metal layer by coating an anti-corrosion solution on the surface of the intermediate metal layer on the side contacting with the thermal welding resin layer and then performing heat treatment at a high temperature for a period of time;
3. and forming and compounding an outer adhesive layer, namely coating polyurethane adhesive dissolved by organic solvent between the middle metal layer and the outer base material resin layer, heating for a certain time at a certain temperature to volatilize the organic solvent to form the outer adhesive layer, further compounding the outer base material resin layer, the outer adhesive layer and the middle metal layer at a certain temperature and pressure, storing for a certain time at a certain temperature, and performing curing reaction on the outer adhesive layer to obtain the composite resin layer consisting of the outer base material resin layer, the outer adhesive layer and the middle metal layer. When the outer-layer adhesive is not used for compounding the outer base material resin layer and the middle metal layer, the middle metal layer and the outer base material resin layer are compounded in a heating and pressurizing mode, and the outer base material resin layer is processed by heating, ultraviolet treatment and electronic wires to be filmed, so that a compound resin layer consisting of the outer base material resin layer and the middle metal layer can be obtained;
4. compounding of the heat-sealing resin layer the composite film composed of the outer base resin layer and the intermediate metal layer may be suitably selected to be compounded with the heat-sealing resin layer in various compounding manners, as exemplified below: a. the dry compounding process includes coating solution type inner layer adhesive comprising main agent, curing agent and organic solvent onto the anticorrosive surface of the middle metal layer of the composite film comprising outer base resin layer and middle metal layer, drying the solution type inner layer adhesive to form the inner layer adhesive layer, heat compounding with the adhering surface of the heat welded resin layer at certain temperature and pressure, and curing to form the composite product of outer base resin layer, middle metal layer, inner layer adhesive layer and heat welded resin layer. Preferably, the adhesive surface of the heat-fusible resin layer in contact with the inner-layer adhesive layer is subjected to corona treatment in advance. In addition, curing treatment at a temperature of 60 ℃ below the melting point of the inner adhesive layer can be performed; b. melt extrusion method, in which a resin for a hot-melt type inner layer adhesive is melt-extruded to form a hot-melt type inner layer adhesive layer having a predetermined thickness on the anti-corrosion surface of the intermediate metal layer. In addition, the surface of the inner layer adhesive layer is thermally compounded with the bonding surface of the thermal welding resin layer to form a composite product of the outer base material resin layer/the middle metal layer/the inner layer adhesive layer/the thermal welding resin layer. In order to improve the peeling force between the middle metal layer and the hot-melt resin layer, heat treatment at a temperature of 60 ℃ below the melting point of the inner adhesive layer can be carried out; c. and a melt extrusion method, wherein the hot-melt type inner layer adhesive layer and the hot-melt resin layer form a composite product of the outer base material resin layer/the middle metal layer/the inner layer adhesive layer/the hot-melt resin layer by a co-extrusion method. After the surface of the intermediate metal layer in contact with the inner adhesive layer is subjected to anti-corrosion treatment, in order to improve the peeling force between the intermediate metal layer and the thermal welding resin layer, heat treatment at a temperature of not more than 60 ℃ higher than the melting point of the inner adhesive layer can be performed; d. the hot-bonding method comprises dissolving resin main agent with melting point above 100 deg.C and curing agent in water or organic solvent to form water solution type inner layer adhesive. The coating is applied to the metal layer anti-corrosion treated surface of the composite layer consisting of the outer base resin layer and the intermediate metal layer, and the solution type inner layer adhesive is dried to form an inner layer adhesive layer. And thermally compounding the adhesive layer with the bonding surface of the thermal welding resin layer at a certain temperature and pressure to form a composite product of the outer base material resin layer/the middle metal layer/the inner layer adhesive layer/the thermal welding resin layer. In order to increase the peeling force between the intermediate metal layer and the heat-fusion resin layer, heat treatment at a temperature of 60 ℃ or less than the melting point of the inner adhesive layer may be performed. The heat-fusible resin layer may be formed by extrusion, or a film may be used, and when a film is used, it is preferable that the adhesive surface of the heat-fusible resin layer in contact with the inner adhesive layer is subjected to corona treatment in advance;
the peel strength between the intermediate metal layer and the thermal fusion resin layer of the finished metal-plastic composite film was tested as follows.
Initial peel strength test:
preparing a finished product of the metal-plastic composite film into a straight strip shape, wherein the size of a sample strip is 100 x 15mm, performing an interlayer peeling test of an intermediate metal layer and a thermal welding resin layer by using a tensile test device, placing a peeled thermal welding resin layer film in an upper clamping plate of the tensile test device, placing the intermediate metal layer in a lower clamping plate, performing T-shaped peeling with a peeling surface of 180 degrees under the condition that the stretching speed is 50mm/min, and starting to measure the peeling strength between the intermediate metal layer and the thermal welding resin layer. The peel strength was read in such a manner that the moving distance of the thermal fusion resin layer and the intermediate metal layer was 50mm, and the average value of the peel strengths between the moving distances of 10mm and 40 mm was selected. 5/group were tested in parallel.
And (3) testing the anhydrous electrolyte resistance of the finished metal-plastic composite film:
directly soaking the metal-plastic composite film finished sample bar in a solution containing 1mol/L LiPF 6 Carbonic acid diMethyl ester (DMC): diethyl carbonate (DEC): the method comprises the following steps of soaking the mixture in a mixed solvent of which the mass ratio of Ethylene Carbonate (EC) substances is 1.
Testing the water and electrolyte resistance of the metal plastic composite film finished product:
cutting the metal-plastic composite film into strips with the width of 15mm and the length of 100mm, stripping the middle metal layer and the hot-melt resin layer for 20mm, and soaking the strips in a solution containing 1mol/L LiPF 6 Dimethyl carbonate (DMC): diethyl carbonate (DEC): adding 1000PPM water accounting for the total mass of the electrolyte into a solvent with Ethylene Carbonate (EC) of 1.
The method for producing the outer packaging material is not particularly limited as long as the anticorrosive layer defined in the present application can be obtained, and a known method for producing an outer packaging material can be used.
The following description is made of a method for producing a device exterior material and a battery having high corrosion resistance, and the present invention is not limited thereto.
1. Compounding
The metal-plastic composite film is composed of an outer base material resin layer/an outer adhesive layer A (3 mu m)/an intermediate metal layer/an inner adhesive layer B/a thermal welding resin layer. The thicknesses of the outer substrate resin layer and the intermediate metal layer may vary according to individual embodiments.
The lamination method is as follows: the outer base resin layer film in contact with the outer adhesive layer a was subjected to corona treatment. Specifically, an amorphous polyester polyol having a weight average molecular weight of 5000, a Tg of 50 ℃ and a hydroxyl value of 25mg KOH/g and an amorphous polyester polyol having a weight average molecular weight of 20000, a Tg of-17 ℃ and a hydroxyl value of 8mg KOH/g were mixed at a weight ratio of 3, toluene Diisocyanate (TDI) was added to form an outer layer binder having an NCO/OH ratio of 6.2, and the outer layer binder was coated on an intermediate metal to form an adhesive layer A (3 μm) on the intermediate metal. The outer adhesive layer A on the intermediate metal and the outer base resin layer film were thermally laminated, followed by aging treatment at 80 ℃ for 3 days to form an outer base resin layer/outer adhesive layer A (3 μm)/intermediate metal layer. Both sides of the intermediate metal layer are previously subjected to an anti-corrosion treatment.
Both sides of the metal layer are pre-treated with corrosion protection.
The anticorrosive liquid used in examples 1 to 9 and comparative example 1 was uniformly coated on both sides of the intermediate metal by a coating roll and then baked at 190 ℃ for 2min, and the wet film coating amount of the anticorrosive layer-treating liquid was 5g/m2.
Comparative examples 2 and 3 heating conditions were set at 100 ℃ for 2 minutes. The wet coating amount of the anticorrosive layer treatment liquid was 5g/m 2 。
Finally, one is to mix the semi-finished product: the metal surface of the outer base material resin layer/the outer layer adhesive layer A (3 mu m)/the middle metal layer is compounded with an inner layer adhesive layer B-1 and a hot-melt resin layer.
Compounding the melting type inner layer adhesive layer B-1: the molten resin used for the inner layer adhesive layer was anhydrous maleic anhydride-modified polypropylene, and an adhesive layer having a thickness of 15 μm was formed on the anti-corrosion treated surface of the intermediate metal layer in contact with the heat-fusible resin layer, and further compounded with a heat-fusible resin having a thickness of 30 μm. The inner adhesive layer and the hot-melt resin layer are compounded on the anti-corrosion treatment surface of the middle metal layer which is contacted with the hot-melt resin layer in a melting and co-extrusion mode. The inner layer adhesive layer used was an anhydrous maleic anhydride-modified random copolymer polypropylene having a melting point of 140 ℃ and an MFR (230 ℃) of 5g/10min (in terms of weight ratio), a degree of modification of the random copolymer polypropylene with anhydrous maleic anhydride of 10%, a melting point of 160 ℃, an MFR (230 ℃) of 2.6g/10min, and a density of 0.87g/cm 3 24% by weight of a propylene/butene copolymer elastomer having a melting point of 130 ℃, an MFR (230 ℃) of 9.5g/10min and a density of 0.91g/cm 3 8% by weight of an ethylene-propylene crystalline copolymer elastomer and a low density having a melting point of 105 ℃ and an MFR (230 ℃) of 12g/10minPolyethylene 8% (by weight) in the mixture.
The hot welding resin layer is composed of two layers, and the structure of the hot welding resin layer is as follows:
resin layer in contact with inner adhesive layer: a mixture layer comprising 62% by weight of a random copolymer polypropylene having a melting point of 155 ℃ and an MFR (230 ℃) of 4g/10min, 33% by weight of an amorphous propylene-based elastomer, and 5% by weight of a low-density polyethylene having a melting point of 110 ℃ and an MFR (230 ℃) of 7.5g/10 min;
innermost resin layer: a layer composed of a random copolymer polypropylene having a melting point of 155 ℃ and an MFR (230 ℃) of 15g/10 min;
the thickness ratio of the resin layer in contact with the inner-layer adhesive layer to the innermost resin layer was 8.
The intermediate metal layer was laminated with the inner adhesive layer and the heat-fusible resin layer, and then heat-treated at 180 ℃ for 2 seconds. Thus, a composite product of the outer base resin layer/outer adhesive layer A (3 μm)/intermediate metal layer/inner adhesive layer B-1 (15 μm)/heat-fusible resin layer (30 μm) was formed.
The other one is to mix the semi-finished product: the metal surface of the outer base resin layer/the outer adhesive layer A (3 mu m)/the middle metal layer is compounded with an inner adhesive layer B-2 and a heat-fusion resin layer.
Solution type inner layer adhesive layer B-2 compounding method: an anhydrous maleic anhydride-modified polypropylene solution having a weight average molecular weight of 80000, a melting point of 80 ℃, and an acid value of 2mg KOH/g and an aromatic isocyanate (HDI-based, hexamethylene diisocyanate) solution were applied to an intermediate metal surface of a composite film having an outer base resin layer, which was brought into contact with a heat-fusion resin layer, which had been subjected to an anti-corrosion treatment, in a solid ratio of 20. The adhesive surface of the 3-layer heat-fusible resin layer in contact with the inner-layer adhesive layer B was subjected to corona treatment in advance.
The three-layer structure of the hot-melt resin is as follows:
resin layer in contact with inner adhesive layer: a layer composed of a random copolymer polypropylene having a melting point of 145 ℃ and an MFR (230 ℃) of 7.5g/10 min;
an intermediate resin layer: a mixture layer comprising 40% by weight of a crystalline polymer elastomer composed of a block copolymer polypropylene having a melting point of 162 ℃ and an MFR (230 ℃) of 2g/10min, 40% by weight of a block copolymer polypropylene having a melting point of 160 ℃ and an MFR (230 ℃) of 5g/10min, and 20% by weight of an ethylene-propylene elastomer having a melting point of 130 ℃, an MFR (230 ℃) of 9.5g/10min, and a density of 0.91g/cm 3;
innermost resin layer: a layer composed of a random copolymer polypropylene having a melting point of 145 ℃ and an MFR (230 ℃) of 7.5g/10 min;
the thickness ratio of three resin layers from the layer in contact with the inner adhesive layer to the innermost layer in the heat-fusion resin layer is 1.
2. The peel strength between the intermediate metal layer and the thermal fusion resin layer of the finished metal-plastic composite film was tested as follows.
(1) Initial peel Strength test
Preparing a metal-plastic composite film finished product into a straight strip shape, wherein the size of a sample strip is 100 x 15mm, performing an interlayer peeling test of an intermediate metal layer and a thermal welding resin layer by using a tensile test device, placing a peeled thermal welding resin layer film in an upper clamping plate of a telescopic test device, placing the intermediate metal layer in a lower clamping plate, performing T-shaped peeling with a peeling surface of 180 degrees under the condition that the telescopic speed is 50mm/min, and starting to measure the peeling strength between the intermediate metal layer and the thermal welding resin layer. The peel strength was read in such a manner that the moving distance of the thermal fusion resin layer and the intermediate metal layer was 50mm, and the average value of the peel strengths between the moving distances of 10mm and 40 mm was selected. 5/group were tested in parallel.
(2) Anhydrous electrolyte resistance test of finished metal-plastic composite film (results are shown in Table 1 for anhydrous electrolyte resistance test)
Directly soaking a metal-plastic composite film finished product sample bar in a solution containing 1mol/L LiPF 6 Dimethyl carbonate (DMC): diethyl carbonate (DEC): the weight ratio of Ethylene Carbonate (EC) material is 1:1, soaking the sample in the mixed solvent at 85 ℃ for 7 days, taking out, washing with water for 15min, wiping off the moisture on the surface of the sample strip, and measuring the peel strength between the intermediate metal layer and the thermal welding resin layer according to the method for testing the initial peel strength.
(3) Water electrolyte resistance test of finished metal-plastic composite film (results shown in Table 1 for Anhydrous electrolyte resistance test)
Stripping the metal/thermal welding resin composite layer of the metal-plastic composite film finished sample bar by 20mm, and soaking the metal/thermal welding resin composite layer in a solution containing 1mol/L LiPF 6 Dimethyl carbonate (DMC): diethyl carbonate (DEC): adding 1000PPM water accounting for the total mass of the electrolyte into a mixed solution of Ethylene Carbonate (EC) substances in a mass ratio of 1. In this test method, the metal layer and the heat-fusible resin layer were peeled off in a state where residual moisture was present therebetween, and the peel strength between the intermediate metal layer and the heat-fusible resin layer was measured from a previously peeled portion.
3. Measurement method
(1) Water contact Angle measurement
Measuring a water contact angle of the metal surface by using a German KRUSS DSA25 contact angle measuring instrument, flatly placing the metal on an instrument workbench, controlling the water yield of the injector to be 2 mu mL each time, controlling the liquid adding speed to be 2.67 mu mL/s, and recording the contact angle value of the metal surface on which the water drops just drop;
(2) Determination of dyne value
Continuously drawing 2 straight lines with the length of 10cm on the metal surface by using a German Architest dyne pen, if the straight line is contracted by more than 10 percent within 3 seconds, indicating that the dyne value of the metal surface cannot reach the dyne value of the dyne pen at the moment, and selecting the dyne pen with the low dyne value for retesting;
(3) Elemental determination of anticorrosive layer
The element distribution of the surface of the anticorrosive layer on the metal surface and the depths of 20nm and 40nm was measured by the ESCA method using XPS (AXIS supra, shimadzu, UK). The method comprises the steps of sputtering the metal surface of a sample by Ar ions, wherein the diameter of an ion beam is 800 mu m, the voltage is 15KV, the sputtering depth of the ion beam is 5nm, the sputtering rate is 3nm/min, the sputtering frequency is 7 times, the detection depth of a signal source is 5nm, the detection limit is 1 per mill, and the detection frequency is 8 times.
The method for manufacturing the liquid-resistant processing sample comprises the following steps: the metal on which the corrosion-preventing layer had been formed was cut into a strip of 20mm wide and 100mm long, and the strip was immersed in a solution containing 1mol/L of LiPF 6 Dimethyl carbonate (DMC): diethyl carbonate (DEC): adding 1000PPM water accounting for the total mass of the electrolyte into a solvent with Ethylene Carbonate (EC) of 1.
Example 1
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The dyne value is 68dyn/cm, both sides of the metal are subjected to corrosion prevention treatment, each layer of elements in the corrosion prevention layers on both sides of the metal account for the ratio shown in table 1, the content ratio of the chromium fluoride, the hydrofluoric acid, the polyvinyl alcohol resin and the zirconium fluoride on the surface of the obtained intermediate metal is 15mg/m 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a mode of B-1.
Example 2
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The water contact angle is 10 degrees, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on the two sides of the metal is shown in the table 1, the content ratio of the chromium nitrate, the phosphoric acid and the acrylic resin on the surface of the obtained intermediate metal is 3 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a mode of B-1.
Example 3
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The dyne value is 75dyn/cm, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is shown in the table 1, the content ratio of the chromium nitrate, the phosphoric acid and the acrylic resin on the surface of the obtained intermediate metal is 3 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Example 4
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The water contact angle is 15 °, both metal surfaces are subjected to anticorrosion treatment, the content of each layer of elements in the anticorrosion layers on both metal surfaces is as shown in table 1, the content ratio of the obtained intermediate metal surface chromium fluoride, hydrofluoric acid, polyvinyl alcohol resin and zirconium fluoride is 15mg/m, and the content of chromium (Cr) coated on the metal surface is 15 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a mode of B-1.
Example 5
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 12 μm. The water contact angle is 20 degrees, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is shown in the table 1, the content ratio of the obtained intermediate metal surface chromium fluoride, hydrofluoric acid, polyvinyl alcohol resin and zirconium fluoride is 15mg/m 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Example 6
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 17 μm. The water contact angle is 20 degrees, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is as shown in the table 1, the content ratio of the obtained intermediate metal surface chromium fluoride, hydrofluoric acid, polyvinyl alcohol resin and zirconium fluoride is 15mg/m 2 。
The inner layer adhesive layer is compounded with the hot-melt resin layer in a B-2 mode.
Example 7
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The water contact angle is 15 degrees, the two sides of the metal are subjected to corrosion prevention treatment, the content of the bridging agent in the used corrosion prevention liquid is 0.06 percent, the content of each layer of elements in the corrosion prevention layers on the two sides of the metal is shown in the table 1, and the obtained chromium fluoride, hydrofluoric acid and polyethylene on the surface of the intermediate metalThe content ratio of the enol resin to the zirconium fluoride is 15 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Example 8
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 2 μm. The water contact angle is 15 degrees, both sides of the metal are subjected to corrosion prevention treatment, the content of the bridging agent in the used corrosion prevention liquid is 8.3 percent, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is shown in the table 1, the content ratio of the chromium nitrate, the phosphoric acid and the acrylic resin on the surface of the obtained intermediate metal is 2 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Example 9
The thickness of the intermediate metal layer is 50 μm, and the thickness of the nickel plating layer is 5 μm. The water contact angle is 15 degrees, the two sides of the metal are subjected to anti-corrosion treatment, the content of the bridging agent in the used anti-corrosion liquid is 14.93 percent, the content of each layer of elements in the anti-corrosion layers on the two sides of the metal is shown in the table 1, the content ratio of the chromium nitrate, the phosphoric acid and the acrylic resin on the surface of the obtained intermediate metal is 2 2 。
The inner layer adhesive layer is compounded with the hot-melt resin layer in a B-2 mode.
Comparative example 1
The thickness of the intermediate metal used was 50 μm and the thickness of the nickel-plated layer was 2 μm. The water contact angle is 15 degrees, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is shown in the table 1, the content ratio of the obtained chromium fluoride, hydrofluoric acid and polyvinyl alcohol resin on the surface of the metal is 2mg/m 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a mode of B-1.
Examples 1 to 9, the peel strength of the metal-plastic composite film was 10.0N/15mm or more, and the peel strength maintenance rates after being left for 7 days in the electrolyte environments of no water and water were 50% or more and 40% or more, respectively, whereas the trivalent chromium compound content of the corrosion preventing liquid used in this comparative example was low.
The carbon (C) content of the surface was 67%, and the element content from the intermediate metal layer was 5.5%. The content of carbon (C) is 0.1% and the content of elements in the intermediate metal layer is 25% and is lower than that of fluorine (F) at a position of 40nm from the surface layer of the anti-corrosion layer to the inner side, and the content of fluorine (F) is 6.7%. And after the electrolyte is soaked for 5 days, the content of fluorine element (F) is up to 27.3 percent at 40 nm.
At this time, the initial strength was 13.85N/15mm, and the electrolyte resistance test maintenance ratios were: the values were 58% without water and 26% with water, both of which were lower than those in examples.
Comparative example 2
The thickness of the used intermediate metal was 50 μm and the thickness of the nickel plating layer was 2 μm. The dyne value is 75dyn/cm, both sides of the metal are subjected to corrosion prevention treatment, the content of each layer of elements in the corrosion prevention layers on both sides of the metal is shown in the table 1, the content ratio of the chromium nitrate, the phosphoric acid and the acrylic resin on the surface of the obtained intermediate metal is 1 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Comparative examples 1 to 9, the heating condition for forming the corrosion prevention layer of this comparative example was 100 ℃ for 2 minutes.
The carbon (C) content of the surface was 38%, and the element content from the intermediate metal layer was 5.2%. The element content of the intermediate metal layer was 22% and was low at 40nm from the surface layer of the corrosion-resistant layer to the inside. And after the electrolyte is soaked for 5 days, the content of fluorine element (F) is up to 28.72 percent at 40 nm.
At this time, the initial strength was 14.68N/15mm, and the maintenance ratio in the electrolyte resistance test was: the values were as low as in examples, 60% without water and 32% with water.
Comparative example 3
The thickness of the intermediate metal used was 50 μm and the thickness of the nickel-plated layer was 0.2. Mu.m. The dyne value is 75dyn/cm, both sides of the metal are subjected to corrosion prevention treatment, the content of the bridging agent in the used corrosion prevention liquid is 25.00 percent, and the corrosion prevention layers on both sides of the metalThe content ratio of the obtained metal surface chromium fluoride, hydrofluoric acid and polyvinyl alcohol resin is 2 2 。
The inner layer adhesive layer is compounded with the hot melt resin layer in a B-2 mode.
Comparative examples 1 to 9, the heating condition for forming the corrosion prevention layer of this comparative example was 100 ℃ for 2 minutes.
The content of carbon (C) on the surface was 66%, the content of the element derived from the intermediate metal layer was 12.4% and higher, and the content of fluorine (F) was 11.7% and higher. The element content of the intermediate metal layer was 89% and the fluorine element (F) content was 22.4% higher at a position 40nm inward from the surface layer of the corrosion-resistant layer.
Figure BDA0003964035170000481
Further, after 5 days of immersion in the electrolyte, the fluorine element (F) content was 26.9% at 40 nm. At this time, the initial strength was 15.11N/15mm, and the electrolyte resistance test maintenance ratios were: 66% without water and 38% with water showed lower values than in the examples.
Although the initial adhesion is fully exerted, the crosslinking density inside the anticorrosive layer is too high due to the ultrahigh content of the bridging agent in the anticorrosive solution, the hardness of the anticorrosive layer is ultrahigh, and the anticorrosive layer is easy to crack due to bending in the liquid-resistant treatment operation process, so that the permeation of the electrolyte is aggravated, and the maintenance rate is low.
Compared with the prior art, the invention has the following positive effects:
the method is characterized in that the intermediate metal layer is made of a nickel-plated steel plate material, elements in the surface anti-corrosion layer are distributed in a gradient manner, and the initial peeling strength between the intermediate metal layer and the hot-melt bonding resin layer of the metal-plastic composite film and the corrosion resistance in the electrolyte environment with more water can be improved by controlling the carbon (C) content of the outermost layer and the intermediate metal element and fluorine (F) content at the inner layer (40 nm) in the anti-corrosion layer; therefore, the invention has excellent corrosion resistance and extremely high industrial utilization value.
The above matters related to the common general knowledge are not described in detail and can be understood by those skilled in the art.
The present invention is not intended to be limited to the particular embodiments shown and described, and any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention are intended to be included within the scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. An electrolyte corrosion resistant outer packaging material for a lithium ion battery device is characterized in that: the anti-corrosion coating comprises an intermediate metal layer and an anti-corrosion layer formed by the intermediate metal layer through corrosion resistance treatment.
2. The outer packaging material according to claim 1, wherein: further comprises an outer base resin layer, an inner adhesive layer and a hot-melt resin layer; the outer base material resin layer is arranged on the middle metal layer, the middle metal layer is arranged on the inner layer adhesive layer, and the inner layer adhesive layer is arranged on the hot-melt resin layer; wherein the corrosion protection layer is disposed between the intermediate metal layer and the inner adhesive layer.
3. The outer package material according to claim 2, wherein: the outer base material resin layer is arranged on the outer adhesive layer, and the outer adhesive layer is arranged on the middle metal layer; wherein the intermediate metal layer is disposed between the outer adhesive layer and the inner adhesive layer.
4. The outer package material according to claim 1, wherein: the middle metal layer is a nickel-plated steel plate, and the thickness of a nickel-plated layer of the nickel-plated steel plate is 0.5-20 mu m.
5. The outer package material according to claim 2, wherein: the carbon component and the metal component of the anti-corrosion layer are distributed in a gradient manner.
6. The outer package material according to claim 2, wherein: the element components on the anti-corrosion layer on the side of the heat welding resin layer are distributed in a gradient manner, the content ratio of carbon (C) on the outermost layer of the anti-corrosion layer on the side of the heat welding resin layer is more than or equal to 40% and less than or equal to 100%, the content ratio of nickel (Ni) is less than or equal to 10%, and the content ratio of fluorine (F) is less than or equal to 10%; in the layer 40nm below the surface layer of the anti-corrosion layer, the content of carbon (C) is less than or equal to 10%, the content of nickel (Ni) is more than or equal to 30% and less than or equal to 100%, and the content of fluorine (F) is less than or equal to 20%.
7. The outer package material according to claim 2, wherein: after the liquid-resistant treatment, in the layer which is arranged at the most surface layer of the anti-corrosion layer at the side of the heat-welding resin layer and is 40nm below, the content ratio of carbon (C) is less than or equal to 10%, the content ratio of nickel (Ni) is greater than or equal to 30%, and the content ratio of fluorine element (F) is less than or equal to 25%.
8. The outer packaging material according to claim 1, wherein: the anti-corrosion layer is formed by drying an anti-corrosion liquid, wherein the anti-corrosion liquid mainly comprises a trivalent chromium compound, an inorganic acid, an organic resin, a bridging agent and a solvent consisting of water or an organic solvent or a mixed solution thereof.
9. The outer packaging material according to claim 8, wherein: the bridging agent contains at least one of amino resin, melamine resin, phenolic resin, epoxy compound, blocked isocyanate compound, oxazoline compound, carbodiimide compound, condensate of formaldehyde and C1-4 alkyl-monohydric alcohol, condensate of carbolic acid and formaldehyde, and derivatives of the above substances.
10. The outer packaging material according to claim 8, wherein: the trivalent chromium compound and the bridging agent in the anti-corrosion liquid used for forming the anti-corrosion layer at least consist of one of chromium nitrate and chromium fluoride: the corrosion preventing solution for forming the corrosion preventing layer contains titanium (Ti) compound or zirconium (Zr) compound in the content of 0-0.6% and 0-2.8%, respectively.
CN202211488919.0A 2022-09-02 2022-11-25 Electrolyte corrosion-resistant outer packaging material for lithium ion battery device Pending CN115851157A (en)

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CN202211079847 2022-09-02

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120118437A1 (en) * 2010-11-17 2012-05-17 Jian Wang Zinc coated steel with inorganic overlay for hot forming
CN105917029A (en) * 2014-01-15 2016-08-31 萨夫罗克有限公司 Method for producing a chromium coating and a coated object
CN112563632A (en) * 2020-12-07 2021-03-26 江西睿捷新材料科技有限公司 Metal composite film and electrochemical device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120118437A1 (en) * 2010-11-17 2012-05-17 Jian Wang Zinc coated steel with inorganic overlay for hot forming
CN105917029A (en) * 2014-01-15 2016-08-31 萨夫罗克有限公司 Method for producing a chromium coating and a coated object
CN112563632A (en) * 2020-12-07 2021-03-26 江西睿捷新材料科技有限公司 Metal composite film and electrochemical device
CN113517504A (en) * 2020-12-07 2021-10-19 江西睿捷新材料科技有限公司 Metal composite film and electrochemical device thereof

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