CN112501597B - Metal-plated thin film material and preparation method and application thereof - Google Patents

Metal-plated thin film material and preparation method and application thereof Download PDF

Info

Publication number
CN112501597B
CN112501597B CN202011387637.2A CN202011387637A CN112501597B CN 112501597 B CN112501597 B CN 112501597B CN 202011387637 A CN202011387637 A CN 202011387637A CN 112501597 B CN112501597 B CN 112501597B
Authority
CN
China
Prior art keywords
solution
film
polymer film
metal
film material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011387637.2A
Other languages
Chinese (zh)
Other versions
CN112501597A (en
Inventor
杨宇
陈柱钻
楚状状
杨卓鸿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China Agricultural University
Original Assignee
South China Agricultural University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China Agricultural University filed Critical South China Agricultural University
Priority to CN202011387637.2A priority Critical patent/CN112501597B/en
Publication of CN112501597A publication Critical patent/CN112501597A/en
Application granted granted Critical
Publication of CN112501597B publication Critical patent/CN112501597B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of battery materials, and particularly relates to a metal-plated thin film material, and a preparation method and application thereof. The metal-plated film material consists of a polymer film and micron-sized metal layers coated on the two side surfaces of the polymer film through chemical bonding. According to the invention, strong oxidant oxidation and 3- (methacryloyloxy) propyl trimethoxy silane and (2-methacryloyloxyethyl) trimethyl ammonium chloride are adopted to crosslink into bonds on the surface of the polymer film, so that more chemical bonds are generated on the surface of the film, and the bonding force of the chemical bonds between the film and the metal layer is stronger, therefore, the metal-plated film material has good mechanical property, and the polymer film and the metal layer can not be separated even if mechanical deformation occurs. The metallized film material of the present invention is particularly suitable as a battery current collector.

Description

Metal-plated thin film material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a metal-plated thin film material, and a preparation method and application thereof.
Background
Current collectors are an essential component of lithium ion batteries and play a crucial role in battery performance. The current collectors of the traditional lithium ion batteries are mainly metal aluminum foils and copper foils, the metal foils have the advantage of good conductivity, but are easy to bend and tear, so that the performance of the batteries is reduced, and the current collectors are usually inactive components, do not contribute to the capacity of the batteries and cause considerable dead weight. Therefore, it is a hot spot in the technical field of battery materials to find a material with good conductivity and mechanical properties and light weight to replace the traditional metal aluminum foil and copper foil as a current collector.
Researches show that the material composed of the metal layer and the polymer substrate has good conductive performance and mechanical performance and light weight. In the prior art, there are flexible current collectors composed of a metal layer and a polymer substrate, such as: the patent application with publication number CN 109817987 a discloses a composite elastic-flexible lithium ion battery electrode material, wherein a current collector of the composite elastic-flexible lithium ion battery electrode material is formed by compounding an elastic polymer substrate and a metal foil through a magnetron sputtering method or a solution method; however, the metal foil has a problem that the metal foil is easily separated when mechanically deformed due to a small bonding force with the substrate. Therefore, the development of a preparation method capable of tightly combining the metal layer and the polymer substrate to prepare a material with good conductivity and mechanical properties and light weight is very important for reducing the self weight of the current collector and realizing a battery with high load capacity and high density.
Disclosure of Invention
According to one aspect of the present invention, there is provided a metallized film material comprising a polymer film and micron-sized metal layers coated on both side surfaces of the polymer film by chemical bonding.
The polymer film of the present invention is preferably any one of polyethylene terephthalate (PET), Polyimide (PI), Polyethylene (PE), polypropylene (PP), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and Polydimethylsiloxane (PDMS), and has a thickness of 1 to 10 μm.
The metal layer of the present invention is preferably any one of copper, gold, silver, nickel, and zinc, and has a thickness of 0.5 to 5 μm.
According to another aspect of the present invention, there is provided a method for preparing the above-mentioned metallized film material, comprising the steps of:
(1) adding the polymer film into an oxidant solution for reaction, thereby grafting hydroxyl on the surface of the film;
(2) taking out the polymer film from the oxidant solution, and then putting the polymer film into a 3- (methacryloyloxy) propyl trimethoxy silane solution for reaction, so that the hydroxyl at one end of the surface of the film is fixed with Si, and a carbon-carbon double bond is reserved at the other end of the surface of the film;
(3) taking out the polymer film from the 3- (methacryloyloxy) propyl trimethoxy silane solution, and then putting the polymer film into a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction, so that the carbon-carbon double bond at one end of the surface of the film is subjected to thermocuring, and a quaternary ammonium bond is reserved at the other end of the surface of the film;
(4) taking the polymer film out of the (2-methacryloyloxyethyl) trimethyl ammonium chloride solution, and then soaking the polymer film into a catalyst solution, so that the quaternary ammonium bonds adsorb the catalyst to prepare for next metallization;
(5) and taking out the polymer film from the catalyst solution, then putting the polymer film into the chemical plating solution for reaction, obtaining a metal-plated film material after the reaction is finished, taking out the metal-plated film material, absorbing water, and drying the metal-plated film material.
In some embodiments, the oxidant solution is a sodium hydroxide solution or a potassium hydroxide solution having a concentration of 4 to 8 mol/L. The oxidizing property of the selected oxidant solution cannot be too weak, otherwise, the oxidizing effect is not good; the oxidizing agent solution should also not be too oxidizing, which would dissolve the polymer film. Therefore, the concentration of the oxidant solution is determined to be 4 to 8mol/L in the present invention.
In some embodiments, the 3- (methacryloyloxy) propyltrimethoxysilane solution is present in a 4% volume ratio and is formulated as: firstly, adding absolute ethyl alcohol, glacial acetic acid and water, and then adding a silane coupling agent KH-570, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid to the water to the silane coupling agent is 95:1:4: 4. For example, 95mL of absolute ethanol, 1mL of glacial acetic acid, and 4mL of water are added, followed by 4mL of the silane coupling agent KH-570. In addition, the volume ratio of the 3- (methacryloyloxy) propyltrimethoxysilane solution can be 3%, 5%, 6% and other values between 3 and 6%, which are not listed. Wherein, the main component of the silane coupling agent KH-570 is 3- (methacryloyloxy) propyl trimethoxy silane.
In some embodiments, the (2-methacryloyloxyethyl) trimethylammonium chloride solution has a concentration of 20 wt% and is formulated by: 26.667g of (2-methacryloyloxyethyl) trimethylammonium chloride with a concentration of 75 wt.% and 0.2g of potassium persulfate were dissolved in water and brought to 100mL with water. Furthermore, the concentration of the (2-methacryloyloxyethyl) trimethylammonium chloride solution can also be 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, and other values between 15 and 25 wt.%, which are not further specified herein.
In some embodiments, the catalyst solution is 1 × 10-3～5×10-3A solution of ammonium chloropalladate or silver nitrate in mol/L.
In some embodiments, when copper plating, the electroless plating solution is NaOH, CuSO4·5H2O、KNaC4H4O6·4H2O and HCHO.
In some embodiments, when nickel plating, the electroless plating solution is Ni2SO4·5H2O, sodium citrate, lactic acid and dimethylamine borane.
The preparation method of the invention preferably comprises the following steps:
(1) adding the polymer film into 4-8mol/L sodium hydroxide solution or potassium hydroxide solution for reaction at 40-60 ℃ for 10-40 minutes;
(2) taking out the polymer film from the sodium hydroxide solution, and then putting the polymer film into 3- (methacryloyloxy) propyl trimethoxy silane solution with the volume ratio of 3-6% for reaction at normal temperature for 30-60 minutes;
(3) taking out the polymer film from the 3- (methacryloyloxy) propyl trimethoxy silane solution, and then putting the polymer film into a 15-25 wt% of (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction at the temperature of 60-90 ℃ for 70-100 minutes;
(4) the polymer film was taken out from the (2-methacryloyloxyethyl) trimethylammonium chloride solution and then placed at 1X 10-3～5×10-3Soaking in a solution of ammonium chloropalladate in mol/L or a solution of silver nitrate at normal temperature for 10-30 minutes;
(5) taking the polymer film from the ammonium chloropalladate solution or the silver nitrate solutionAnd (3) taking out, then putting into the chemical plating solution for reaction, obtaining a metal-plated thin film material after the reaction is finished, taking out, absorbing water, and drying. The composition of the electroless plating solution depends on the metal to be plated on the polymer film, such as: when in copper plating, the film is immersed in NaOH and CuSO4·5H2O、KNaC4H4O6·4H2Reacting in solution composed of O and HCHO for 40-60 minutes; when nickel plating is carried out, the film is soaked in Ni2SO4·5H2Reacting in solution composed of O, sodium citrate, lactic acid and dimethylamine borane for 40-60 minutes, and adding ammonia water to adjust the pH value to 7-9.
According to a further aspect of the present invention there is provided the use of a metallised film material as described above as a battery current collector.
Drawings
FIG. 1 is a photograph of a PET film of example 1 of the present invention before metallisation;
FIG. 2 is a photograph of a PET film of example 1 of the present invention after being plated with copper metal;
FIG. 3 is an XRD pattern of a metallized film material of example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of the plane of a metallized film material of example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of a cross-section of a metallized film material of example 1 of the present invention;
FIG. 6 is a photograph of a PI film of example 2 of the present invention before metallization;
FIG. 7 is a photograph of the PI film of example 2 of the present invention after being plated with nickel metal;
FIG. 8 is a photograph of a metallized film material of comparative example 1;
FIG. 9 is a photograph of the metallized film material of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. The materials referred to in the following examples are commercially available.
Example 1
The preparation method of the metal-plated thin film material comprises the following steps:
(1) adding a polyethylene terephthalate (PET) polymer film into a 5mol/L sodium hydroxide solution for reaction at a reaction temperature of 60 ℃ for 15 minutes, and turning over the film for about 5 times during the reaction to ensure that the surface of the film fully reacts with the sodium hydroxide solution;
(2) adding 96mL of absolute ethyl alcohol, 1mL of glacial acetic acid and 4mL of deionized water, and then adding 4mL of silane coupling agent KH-570 to obtain a 4% by volume 3- (methacryloyloxy) propyl trimethoxysilane solution; taking out the polymer film from the sodium hydroxide solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into the 3- (methacryloyloxy) propyl trimethoxy silane solution for reaction at normal temperature for 1 hour, and turning over the film for about 5 times during the reaction, so that the surface of the film is fully reacted with the 3- (methacryloyloxy) propyl trimethoxy silane solution;
(3) measuring 26.7g of (2-methacryloyloxyethyl) trimethyl ammonium chloride with the concentration of 75 wt.% and 0.2g of potassium persulfate, dissolving the mixture with deionized water, and then fixing the volume to 100mL to obtain a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution with the concentration of 20 wt%; taking the polymer film out of the 3- (methacryloyloxy) propyl trimethoxy silane solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction at the reaction temperature of 80 ℃ for 80 minutes, wherein the solution is changed into viscous liquid during the reaction and bubbles are generated;
(4) 0.146g of (NH)4)2PdCl4Dissolving with deionized water, and diluting to 100mL to obtain 5 × 10-3mol/L of (NH)4)2PdCl4A solution; taking the polymer film out of the (2-methacryloyloxyethyl) trimethyl ammonium chloride solution, cooling to room temperature, washing with deionized water for about 3 times, and then soaking in an ammonium chloropalladate solution at room temperature for 30 minutes;
(5) 2.9g of KNaC4H4O6·4H2O、1.3g CuSO4·5H2Dissolving O and 1.2g NaOH in small amount of deionized water respectively, and mixingMixing the two solutions together, fixing the volume to 100mL, marking as a solution A, fixing the volume of 2.5mL of formaldehyde with the concentration of 38 wt.% to 100mL by using deionized water, marking as a solution B, and mixing the solution A and the solution B together to obtain the copper electroless plating solution; taking out the polymer film from the ammonium chloropalladate solution, washing the polymer film for about 5 times by deionized water, wherein each time lasts for about 3 minutes, then putting the polymer film into a copper electroless plating solution for reaction for 15 minutes, turning over the polymer film for about 5 times in the reaction process to ensure that the film is fully reacted, changing the color of the electroless plating solution from dark blue to light blue and changing the color of the film into yellow in the reaction process to obtain a plated metal film material, taking out the plated metal film material, washing the plated metal film material once by deionized water, and then absorbing the water for 3 times by using water-absorbing non-woven fabrics.
The photograph of the film before metallising is shown in figure 1, from which figure 1 it can be seen that the non-metallised PET film is silver grey. The photograph of the film plated with copper is shown in FIG. 2. it can be seen from FIG. 2 that the PET film plated with copper is yellow, and thus it can be seen that the film has been successfully plated with copper and the copper metal layer is uniformly distributed on the film. In addition, XRD test was performed on the PET film after copper metal plating, and as a result, as shown in FIG. 3, it can be seen from FIG. 3 that three characteristic peaks of 44.3, 51.4 and 75.4 were consistent with those of copper, and the other peaks were peaks of the film base, which confirmed that copper was successfully plated on the polymer film.
The scanning electron micrograph of the plane of the metallized film material of this example is shown in FIG. 4, and the scanning electron micrograph of the cross section is shown in FIG. 5. As can be seen from FIG. 4, the plane of the metallized film material of this example is very flat, which shows that the formed metallized film is very uniform; as can be seen from FIG. 5, the thickness of the plated thin film material of the present embodiment is about 5 μm, and the thickness of the copper metal layers on both sides is 1.55 μm each because the thickness of the thin film substrate is 1.9 μm, thereby showing that the plated thin film material of the present invention is very thin and light, and the self weight of the current collector can be greatly reduced by using it as the current collector of the battery.
Example 2
The preparation method of the metal-plated thin film material comprises the following steps:
(1) adding a Polyimide (PI) polymer film into 5mol/L sodium hydroxide solution for reaction at the temperature of 60 ℃ for 10 minutes, and turning over the film for about 5 times during the reaction to ensure that the surface of the film fully reacts with the sodium hydroxide solution;
(2) adding 96mL of absolute ethyl alcohol, 1mL of glacial acetic acid and 4mL of deionized water, and then adding 4mL of silane coupling agent KH-570 to obtain a 4% by volume 3- (methacryloyloxy) propyl trimethoxysilane solution; taking out the polymer film from the sodium hydroxide solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into the 3- (methacryloyloxy) propyl trimethoxy silane solution for reaction at normal temperature for 1 hour, and turning over the film for about 5 times during the reaction, so that the surface of the film is fully reacted with the 3- (methacryloyloxy) propyl trimethoxy silane solution;
(3) measuring 26.7g of (2-methacryloyloxyethyl) trimethyl ammonium chloride with the concentration of 75 wt.% and 0.2g of potassium persulfate, dissolving the mixture with deionized water, and then fixing the volume to 100mL to obtain a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution with the concentration of 20 wt%; taking the polymer film out of the 3- (methacryloyloxy) propyl trimethoxy silane solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction at the reaction temperature of 80 ℃ for 80 minutes, wherein the solution is changed into viscous liquid during the reaction and bubbles are generated;
(4) 0.146g of (NH)4)2PdCl4Dissolving with deionized water, and diluting to 100mL to obtain 5 × 10-3mol/L of (NH)4)2PdCl4A solution; taking the polymer film out of the (2-methacryloyloxyethyl) trimethyl ammonium chloride solution, cooling to room temperature, washing with deionized water for about 3 times, and then soaking in an ammonium chloropalladate solution at room temperature for 30 minutes;
(5) 86.7g of Ni2SO4·6H2Dissolving O, 40.8g of trisodium citrate and 22.22g of lactic acid by using a small amount of deionized water respectively, mixing together, diluting to 1000mL, marking as solution C, dissolving 1.5g of dimethylamine borane by using 15mL of deionized water, and marking as solution D; taking out the polymer film from the ammonium chloropalladate solution, washing with deionized water for about 5 times, each timeAnd (3) putting the film into the solution C for about 3 minutes, adding 1.5mL of the solution D every 3 minutes, dropwise adding 2mL of ammonia water, continuously sucking the electroless plating solution by using a dropper in the reaction process, pouring the electroless plating solution on the film, and discharging air bubbles in time, wherein the color of the electroless plating solution changes from dark green to bright green in the reaction process, the film changes into metal silvery white to obtain a plated metal film material, taking out the plated metal film material, washing the plated metal film material once by using deionized water, and then absorbing water for 3 times by using water-absorbing non-woven fabrics.
The photograph of the film before metallisation is shown in figure 6, and from figure 6 it can be seen that the unmetalised PI film is pale green. The photograph of the film after being plated with nickel is shown in fig. 7, and it can be seen from fig. 7 that the PI film after being plated with nickel is silvery white, so that the film is successfully plated with metal nickel, and the distribution of the nickel metal layer on the film is uniform.
Comparative example 1
The preparation method of the metal-plated film material of the comparative example comprises the following steps:
(1) adding a polyethylene terephthalate (PET) polymer film into 2mol/L sodium hydroxide solution for reaction, wherein the reaction temperature is 60 ℃, the reaction time is 20 minutes, and the film is turned over for about 5 times during the reaction, so that the surface of the film is fully reacted with the sodium hydroxide solution;
(2) adding 96mL of absolute ethyl alcohol, 1mL of glacial acetic acid and 4mL of deionized water, and then adding 4mL of silane coupling agent KH-570 to obtain a 4% by volume 3- (methacryloyloxy) propyl trimethoxysilane solution; taking out the polymer film from the sodium hydroxide solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into the 3- (methacryloyloxy) propyl trimethoxy silane solution for reaction at normal temperature for 1 hour, and turning over the film for about 5 times during the reaction, so that the surface of the film is fully reacted with the 3- (methacryloyloxy) propyl trimethoxy silane solution;
(3) measuring 26.7g of (2-methacryloyloxyethyl) trimethyl ammonium chloride with the concentration of 75 wt.% and 0.2g of potassium persulfate, dissolving the mixture with deionized water, and then fixing the volume to 100mL to obtain a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution with the concentration of 20 wt%; taking the polymer film out of the 3- (methacryloyloxy) propyl trimethoxy silane solution, washing the polymer film for about 3 times by using deionized water, then putting the polymer film into a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction at the reaction temperature of 80 ℃ for 80 minutes, wherein the solution is changed into viscous liquid during the reaction and bubbles are generated;
(4) 0.146g of (NH)4)2PdCl4Dissolving with deionized water, and diluting to 100mL to obtain 5 × 10-3mol/L of (NH)4)2PdCl4A solution; taking the polymer film out of the (2-methacryloyloxyethyl) trimethyl ammonium chloride solution, cooling to room temperature, washing with deionized water for about 3 times, and then soaking in an ammonium chloropalladate solution at room temperature for 30 minutes;
(5) 2.9g of KNaC4H4O6·4H2O、1.3g CuSO4·5H2Dissolving O and 1.2g NaOH with a small amount of deionized water respectively, mixing together, fixing the volume to 100mL, marking as a solution A, fixing the volume of 2.5mL of formaldehyde with the concentration of 38 wt.% to 100mL with deionized water, marking as a solution B, and mixing the solution A and the solution B together to obtain the copper chemical plating solution; taking out the polymer film from the ammonium chloropalladate solution, washing the polymer film for about 5 times by deionized water, wherein each time lasts for about 3 minutes, then putting the polymer film into a copper electroless plating solution for reaction for 15 minutes, turning over the polymer film for about 5 times in the reaction process to ensure that the film is fully reacted, changing the color of the electroless plating solution from dark blue to light blue and changing the color of the film into yellow in the reaction process to obtain a plated metal film material, taking out the plated metal film material, washing the plated metal film material once by deionized water, and then absorbing the water for 3 times by using water-absorbing non-woven fabrics.
A photograph of the metallized film material of comparative example 1 is shown in fig. 8. In fig. 8, the copper metal layer is not uniformly distributed on the film and may be peeled off. In contrast, the comparative example 1 differs from the example 1 only in the concentration of sodium hydroxide in the step (1), and therefore suggests that the oxidizing effect of the oxidizing agent solution with the concentration of 5mol/L is better, more chemical bonds are generated on the surface of the film, and the bonding force of the chemical bonds between the film and the metal layer is stronger, so that the copper metal layer is uniformly distributed on the film and does not fall off.
Comparative example 2
The preparation method of the metal-plated film material of the comparative example comprises the following steps:
(1) adding a polyethylene terephthalate (PET) polymer film into a 5mol/L sodium hydroxide solution for reaction at a reaction temperature of 60 ℃ for 20 minutes, and turning over the film for about 5 times during the reaction to ensure that the surface of the film fully reacts with the sodium hydroxide solution;
(2) taking out the polymer film from a sodium hydroxide solution, washing the polymer film for about 3 times by deionized water, then adding 8g of PEI aqueous solution (70000 molecular weight 50% aqueous solution) into the film, diluting the PEI aqueous solution to 100mL by using methanol, placing the diluted PEI aqueous solution in a 35 ℃ water bath for heating for 24 hours, then adding 25% glutaraldehyde aqueous solution, reacting for 6 hours, continuously washing the film by using a suction tube in the early stage, standing in the later stage, taking out the film after the reaction is finished, and washing the film by using the deionized water for about 5 times to remove unreacted glutaraldehyde and PEI;
(3) 0.0425g of AgNO30.8325g of ethylene glycol and 1.665g of ethanol are dissolved in water, and the volume is determined to be 50mL to obtain AgNO3Solution, then placing the film into AgNO3Soaking the film in the solution for 30 minutes, taking out the film after the reaction is finished, and washing the film for about 5 times by using deionized water;
(4) 2.9g of KNaC4H4O6·4H2O、1.3g CuSO4·5H2Dissolving O and 1.2g NaOH with a small amount of deionized water respectively, mixing together, fixing the volume to 100mL, marking as a solution A, fixing the volume of 2.5mL of formaldehyde with the concentration of 38 wt.% to 100mL with deionized water, marking as a solution B, and mixing the solution A and the solution B together to obtain the copper chemical plating solution; and (2) putting the polymer film into the copper electroless plating solution for reaction for 15 minutes, turning for about 5 times in the reaction process to ensure that the film fully reacts, changing the color of the electroless plating solution from dark blue to light blue and changing the film into yellow in the reaction process to obtain a plated metal film material, taking out the plated metal film material, washing the plated metal film material once with deionized water, and then absorbing water for 3 times with water-absorbing non-woven fabrics.
A photograph of the metallized film material of comparative example 2 is shown in fig. 9. In fig. 9, the copper metal layer is not uniformly distributed on the film and may be peeled off. It is suggested that the method of crosslinking the PEI aqueous solution and the glutaraldehyde aqueous solution on the surface of the film to form bonds results in too few chemical bonds on the surface of the film and too weak bonding force with the metal layer, so that the metal layer is not uniformly plated and may be peeled off.
In conclusion, the invention uses strong oxidant oxidation, 3- (methacryloyloxy) propyl trimethoxy silane and (2-methacryloyloxyethyl) trimethyl ammonium chloride to form bonds on the surface of the polymer film through crosslinking, so that more chemical bonds are generated on the surface of the film, and the bonding force of the chemical bonds between the film and the metal layer is stronger, therefore, the metal-plated film material has better mechanical property, and the polymer film and the metal layer can not be separated even if mechanical deformation occurs.
The invention relates to a metal-plated film material, which is characterized in that two metal layers with the thickness of 0.5-5 microns are coated on two sides of a polymer film through the action of chemical bonds, the polymer film is arranged in the middle, two ultrathin outer metal layers are used as conductive materials, and a conductive metal layer is formed on the surface of the film; the film has light weight, and the weight of the current collector can be reduced by using the film as the current collector of the battery, so that the ultra-light current collector is realized, and the battery can load more active substances, reduce the load of inactive ingredients, reduce the self-weight loss and enable the battery with high load capacity and high energy density to become possible; and the toughness of the film is better than that of metal, so that the toughness of the current collector can be effectively improved, the electrode material can be stabilized, and the battery performance can be improved. More importantly, the metal-plated film material has strong bonding force of chemical bonds between the film and the metal layer and good mechanical property, and the polymer film and the metal layer can not be separated even if mechanical deformation occurs, so the metal-plated film material is particularly suitable for being used as a battery current collector.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.

Claims (6)

1. A metal-plated film material is characterized by consisting of a polymer film and micron-sized metal layers coated on the surfaces of the two sides of the polymer film through chemical bonding, wherein the polymer film is any one of polyethylene glycol terephthalate, polyimide, polyethylene, polypropylene, polyacrylonitrile, polymethyl methacrylate and polydimethylsiloxane, and the thickness of the polymer film is 1-10 mu m; the metal layer is any one of copper, gold, silver, nickel and zinc, and the thickness of the metal layer is 0.5-5 mu m; the preparation method of the metal-plated thin film material comprises the following steps:
(1) adding the polymer film into an oxidant solution for reaction; the oxidant solution is a sodium hydroxide solution or a potassium hydroxide solution with the concentration of 4-8 mol/L;
(2) taking out the polymer film from the oxidant solution, and then putting the polymer film into a 3- (methacryloyloxy) propyl trimethoxy silane solution for reaction;
(3) taking the polymer film out of the 3- (methacryloyloxy) propyl trimethoxy silane solution, and then putting the polymer film into a (2-methacryloyloxyethyl) trimethyl ammonium chloride solution for reaction;
(4) taking out the polymer film from the (2-methacryloyloxyethyl) trimethyl ammonium chloride solution, and then putting the polymer film into a catalyst solution for soaking;
(5) and taking the polymer film out of the catalyst solution, then putting the polymer film into the chemical plating solution for reaction, and obtaining the metal-plated film material after the reaction is finished.
2. The metallized film material of claim 1, wherein the 3- (methacryloyloxy) propyltrimethoxysilane solution is prepared by the following steps: adding absolute ethyl alcohol, glacial acetic acid and water, and then adding 3- (methacryloyloxy) propyl trimethoxy silane, wherein the volume ratio of the absolute ethyl alcohol to the glacial acetic acid to the water to the 3- (methacryloyloxy) propyl trimethoxy silane is 95:1:4: 4.
3. The metallized film material of claim 1, wherein said (2-methacryloyloxyethyl) trimethylammonium chloride solution is prepared by: 26.667g of 75 wt.% of (2-methacryloyloxyethyl) trimethylammonium chloride and 0.2g of potassium persulfate were dissolved in water and brought to 100 mL.
4. The metallized film material according to claim 1, wherein the electroless plating solution is NaOH, CuSO or the like when plating copper4·5H2O、KNaC4H4O6·4H2O and HCHO.
5. The metallized film material of claim 1, wherein the electroless plating solution is Ni when nickel is plated2SO4·5H2O, sodium citrate, lactic acid and dimethylamine borane.
6. Use of a metallized film material according to any one of claims 1 to 5 as a current collector for a battery.
CN202011387637.2A 2020-12-01 2020-12-01 Metal-plated thin film material and preparation method and application thereof Active CN112501597B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011387637.2A CN112501597B (en) 2020-12-01 2020-12-01 Metal-plated thin film material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011387637.2A CN112501597B (en) 2020-12-01 2020-12-01 Metal-plated thin film material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112501597A CN112501597A (en) 2021-03-16
CN112501597B true CN112501597B (en) 2021-09-07

Family

ID=74969088

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011387637.2A Active CN112501597B (en) 2020-12-01 2020-12-01 Metal-plated thin film material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112501597B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114864953A (en) * 2022-05-13 2022-08-05 扬州纳力新材料科技有限公司 Low-swelling composite current collector and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546727A (en) * 2003-12-11 2004-11-17 南京大学 Chemical plating nickel conductive film on polymer thin film surface and method for preparing the same
US7255782B2 (en) * 2004-04-30 2007-08-14 Kenneth Crouse Selective catalytic activation of non-conductive substrates
CN107012450A (en) * 2017-04-21 2017-08-04 中国科学院深圳先进技术研究院 A kind of method of polymeric substrate surface metallization and application thereof
CN111446453A (en) * 2020-04-29 2020-07-24 国家纳米科学中心 Flexible conductive film and preparation method and application thereof
CN111876743A (en) * 2020-09-05 2020-11-03 昆山鑫美源电子科技有限公司 Production and processing system and preparation process of flexible conductive film

Also Published As

Publication number Publication date
CN112501597A (en) 2021-03-16

Similar Documents

Publication Publication Date Title
CN105556004B (en) Copper foil, copper foil and copper clad laminate with carrier foils
KR20070094624A (en) Metal film and formation method of metal film
CN112501597B (en) Metal-plated thin film material and preparation method and application thereof
Mao et al. Electroless silver plated flexible graphite felt prepared by dopamine functionalization and applied for electromagnetic interference shielding
CN1422741A (en) Method for forming resin composite material
WO2010098452A1 (en) Negative electrode active material for lithium ion secondary battery, and lithium ion secondary battery
TWI276117B (en) Coated conductive particle, conductive material, anisotropic conductive adhesive and anisotropic conductive junction structure
CN114369955B (en) Method for preparing high-performance electromagnetic shielding paper by using carbon fiber
KR101423169B1 (en) A Method for Manufacturing of Shield Sheet for Preventing Electromagnetic Wave
CN113286917B (en) Copper foil, negative electrode current collector for lithium ion battery containing copper foil, and method for producing same
WO2010073882A1 (en) Method for producing multilayer wiring substrate
WO2011090153A1 (en) Copper surface treatment agent
US20180208792A1 (en) Film coating and film coating compositions for surface modification and metallization
CN114520399A (en) Water-based battery composite diaphragm and preparation method and application thereof
CN110004436B (en) Passivation solution, treated copper foil and lithium battery packaging film containing copper foil
CN117334926B (en) Composite current collector and preparation method and application thereof
CN117042334B (en) Silver plating lamination method for printed circuit board substrate
KR101960588B1 (en) Composition of thin film using Conductive Metal Ink and Method for preparing the same
CN110634589A (en) Polydopamine-coated graphene oxide-based ternary artificial pearl layer material and preparation method thereof
CN113943954B (en) Preparation method of 2-3 micron pinhole-free carrier electrolytic copper foil
CN116791160A (en) Preparation method of high heat-resistant electrolytic copper foil
TW202106931A (en) Composite copper member
US20150155572A1 (en) Flexible fuel cell and method of manufacturing the same
JP2008075146A (en) METHOD FOR PRODUCING Ni THIN FILM
JP4029717B2 (en) Carbon electrode for polymer battery and battery using the electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant