CN108400339B - Preparation method and application of nickel cloth current collector - Google Patents

Preparation method and application of nickel cloth current collector Download PDF

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CN108400339B
CN108400339B CN201810167221.6A CN201810167221A CN108400339B CN 108400339 B CN108400339 B CN 108400339B CN 201810167221 A CN201810167221 A CN 201810167221A CN 108400339 B CN108400339 B CN 108400339B
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solution
nickel
concentration
chloride
current collector
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CN108400339A (en
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万厚钊
王浩
王聪
甘億
张军
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Hubei University
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/68—Current collectors characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H01G11/70—Current collectors characterised by their structure
    • 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
    • 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
    • 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
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention relates to a preparation method and application of a nickel cloth current collector, and belongs to the technical field of flexible current collectors. The preparation method of the invention takes gauze as a substrate, and sequentially carries out the processes of coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment on the substrate, so that the metal conductive nickel layer is uniformly coated on the fiber of the substrate, thereby preparing the nickel cloth current collector. The method for sensitizing and activating the pure cotton absorbent gauze by using the one-step method can greatly simplify the operation procedure and improve the qualification rate of products, and adopts the normal-temperature alkaline chemical plating solution, thereby avoiding the plating solution waste caused by the instability of the plating solution under the high-temperature condition, being beneficial to the maintenance of the solution and being convenient for operation. In addition, the lithium ion battery and the super capacitor prepared by the nickel cloth current collector have small interface internal resistance, high energy density and high pseudocapacitance, greatly improve the production efficiency of the battery, reduce the production cost and are suitable for industrial large-scale production.

Description

Preparation method and application of nickel cloth current collector
Technical Field
The invention belongs to the technical field of flexible current collectors, and particularly relates to a preparation method of a nickel cloth current collector and application of the nickel cloth current collector in flexible lithium ion batteries and flexible super capacitors.
Background
The current collector, which refers to a structure or a part for collecting current, in a lithium ion battery, mainly refers to a metal foil, such as a copper foil or an aluminum foil, and may also include tabs, and functions to mainly bear active materials and collect current generated from the active materials of the battery so as to form a larger current to be output to the outside, so that the current collector should be in full contact with the active materials, and the internal resistance should be as small as possible.
The current collector of the conventional lithium ion battery is made of metal conductor materials such as copper, aluminum, nickel, stainless steel and the like, semiconductor materials such as carbon and the like and composite materials, wherein metal foils are taken as main materials. The positive electrode current collector of the lithium battery adopts aluminum foil with the thickness of about 14 mu m, and the negative electrode current collector adopts copper foil with the thickness of about 8 mu m. The metal foil has good conductive performance, but the mechanical performance is poor at the thickness, the metal foil is brittle as a whole and has insufficient toughness, irreversible traces and even holes can be generated once the metal foil is impacted by external force or deformed by the external force, the performance and the efficiency of the whole battery are influenced, and a safety problem can be caused in severe cases. In addition, the traditional current collector material has the defects of high price, high production cost, low production efficiency and the like. In recent years, with the rapid development of personalized electronic technology, the development of flexible energy storage devices such as lithium ion batteries and super capacitors has received great attention. It is well known that fiber-based electrodes have relatively high mechanical stability, higher surface area and lighter weight than other conventional electrodes, and that flexible energy storage devices designed with fiber/fabric-based low-cost electrodes have high end-use performance and great potential for development.
The patent application with the application number of 201610164729.1 discloses a conductive non-woven fabric and a preparation method and application thereof, wherein a non-woven fabric substrate is soaked in a catalyst solution, then the soaked non-woven fabric substrate is placed in a metal plating solution for chemical deposition to obtain the conductive non-woven fabric, and then the conductive non-woven fabric is washed and post-treated to obtain a final product. The conductive non-woven fabric layer prepared by the method is uniform and excellent in conductivity, and still has good flexibility of the original non-woven fabric substrate. The ultrathin lithium ion battery assembled by using the lithium ion battery current collector is light and thin in appearance and excellent in performance. In addition, the patent application with the application number of 201710189749.9 discloses a flexible current collector, an electrode containing the flexible current collector and a battery, wherein the flexible current collector comprises a textile fabric substrate and a metal conductive coating, the metal conductive coating is coated on fibers of the textile fabric substrate, the thickness of the metal conductive coating is 200 nm-500 μm, the current collector has better machining performance compared with the traditional metal foil, the production efficiency of the battery can be improved, the production cost is reduced, and the current collector substrate is made of a high polymer material and can be shrunk and fused at high temperature, so that the safety performance of the battery is improved. Among them, the patent with application No. 201610164729.1 adopts an electrodeposition method to coat a layer of simple metal on a non-woven fabric substrate, and the patent with application No. 201710189749.9 adopts a vacuum sputtering method to coat a layer of simple metal on a woven fabric substrate, but both methods are complicated to operate and expensive, and are not beneficial to the commercial production of batteries.
Disclosure of Invention
The invention aims to solve the problems pointed out in the background art and the defects in the prior art, and aims to provide a preparation method and application of a nickel cloth current collector.
In order to achieve the first object of the present invention, through a great deal of experimental research, the inventors have developed a method for preparing a nickel cloth current collector, in which a gauze is used as a substrate, and the substrate is sequentially subjected to roughening, sensitizing, activating, reducing, chemical nickel plating and post-treatment processes, so that a metal conductive nickel layer is uniformly coated on fibers of the substrate, the method specifically includes the following steps:
(1) roughening the substrate: and (2) soaking the substrate material in a roughening solution for 20-30 min at 70 ℃, and then washing with deionized water to obtain the roughened substrate material, wherein the roughening solution is a sodium hydroxide aqueous solution, and the concentration of sodium hydroxide in the roughening solution is 150-200 g/L.
(2) Sensitization and activation: soaking the roughened substrate material in the step (1) in a sensitizing and activating solution for 5-10 min at room temperature, and then washing with deionized water to obtain the sensitized and activated substrate material, wherein the sensitizing and activating solution is a mixed solution composed of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid, the concentration of palladium chloride in the sensitizing and activating solution is 0.15-0.2 g/L, the concentration of stannous chloride is 10-15 g/L, the concentration of sodium chloride is 150-170 g/L, and the concentration of hydrochloric acid is 5-10 ml/L;
(3) reduction: soaking the sensitized and activated substrate material in a reducing solution for 2-5 min at room temperature, and then washing with deionized water to obtain the reduced substrate material, wherein the reducing solution is an aqueous solution of sodium hypophosphite, and the concentration of the sodium hypophosphite in the reducing solution is 25-30 g/L;
(4) chemical nickel plating: at room temperature, placing the reduced substrate material obtained in the step (3) in an electroless plating solution for reaction for 10-20 min to plate a metal nickel layer on the surface of the substrate, wherein the electroless plating solution is a mixed solution composed of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the electroless plating solution is 20-25 g/L, the concentration of the trisodium citrate is 10-15 g/L, the concentration of the sodium hypophosphite is 25-30 g/L, the concentration of the ammonium chloride is 25-30 g/L, and the pH value of the electroless plating solution is 8.5-9.5;
(5) and (3) post-treatment: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at the temperature of 120 ℃ for hydrothermal reaction for 8 hours, taking out the substrate material, washing and drying the substrate material by using deionized water and absolute ethyl alcohol to obtain the nickel cloth current collector, wherein the mixed solution consists of cobalt chloride and/or nickel chloride hexahydrate, Hexamethylenetetramine (HMT) and deionized water, and the molar ratio of the cobalt chloride and/or nickel chloride hexahydrate to the hexamethylenetetramine is 3: 5, the molar volume ratio of the hexamethylene tetramine to the deionized water is 1 mmol: 6 mL.
Further, in the technical scheme, the gauze is pure cotton absorbent gauze.
Further, in the above technical solution, the soaking time in step (2) is preferably 5min, and the electroless plating time in step (4) is preferably 15 min.
Further, in the sensitization activation liquid in the step (2) of the technical scheme, the concentration of palladium chloride is preferably 0.18g/L, the concentration of stannous chloride is preferably 12g/L, the concentration of sodium chloride is preferably 160g/L, and the concentration of hydrochloric acid is preferably 10 ml/L.
Further, in the step (5) of the above technical solution, the mixed solution preferably consists of cobalt chloride, nickel chloride hexahydrate, hexamethylenetetramine and deionized water, and the molar ratio of cobalt chloride to nickel chloride hexahydrate to hexamethylenetetramine is 2: 1: 5.
furthermore, the sensitizing and activating solution in the step (2) of the technical scheme is prepared by the following method:
(a) at room temperature, dissolving palladium chloride in a small amount of concentrated hydrochloric acid according to a ratio to prepare a solution A;
(b) preparing mixed solution from concentrated hydrochloric acid and deionized water according to the volume ratio of 1:2 at room temperature, and dissolving stannous chloride in the mixed solution according to the proportion to prepare solution B;
(c) respectively heating the solution A and the solution B to 70 ℃, keeping the temperature constant, and mixing the solution A and the solution B under the stirring condition to obtain a solution C;
(d) dissolving sodium chloride in deionized water according to a ratio to prepare a solution D, heating the solution D to 60 ℃, keeping the temperature constant, mixing the solution D and the solution C under a stirring condition to obtain a solution E, diluting the solution E to a specified volume, shaking up, and filtering for later use.
Further, in the chemical plating solution in the step (4) of the technical scheme, the concentration of nickel sulfate hexahydrate is preferably 20g/L, the concentration of trisodium citrate is preferably 10g/L, the concentration of sodium hypophosphite is preferably 30g/L, and the concentration of ammonium chloride is preferably 30 g/L.
Furthermore, the electroless plating solution in the technical scheme is prepared by the following method:
(i) weighing raw materials of each component according to a ratio, uniformly dispersing the raw materials in deionized water, and filtering to obtain a single-component concentrated solution;
(ii) adding a concentrated trisodium citrate solution into a chemical plating bath, diluting, then sequentially adding a concentrated ammonium chloride solution, a concentrated nickel sulfate solution and a concentrated sodium hypophosphite solution under the condition of stirring, uniformly stirring, diluting to a specified volume, and finally adjusting the pH value of the chemical plating bath by using a sodium hydroxide solution.
The invention also aims to provide application of the current collector prepared by the method.
The invention provides a composite electrode, which comprises the nickel cloth current collector and NiCo double-metal hydroxide.
The invention also provides a flexible lithium ion battery, which comprises the composite electrode as a positive electrode material.
The invention also provides a flexible supercapacitor, which contains the composite electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for sensitizing and activating the purified cotton absorbent gauze by the one-step method can greatly simplify the operation procedure, reduce the cost and improve the qualification rate of the product;
(2) the method adopts the normal-temperature alkaline chemical plating solution, avoids the waste of the plating solution caused by the instability of the plating solution under the high-temperature condition, is beneficial to the maintenance of the solution and is convenient to operate;
(3) the invention adopts the chemical nickel plating process method, can obtain the nickel cloth with even plating layer and high tensile strength in a short time, the prepared nickel cloth not only keeps the flexibility of the pure cotton absorbent gauze, but also has higher tensile strength and toughness, so that the tension and pressure window in the preparation process are increased, higher pressure can be adopted in the production to realize higher compaction density, and the manufacturing capacity in the process is enhanced; the nickel cloth prepared by the method has higher pseudo capacitance and smaller interface internal resistance, the production efficiency of the battery is greatly improved, and the production cost is reduced;
(4) the electrode prepared by the nickel cloth current collector has the advantages that the specific surface area of the flexible nickel cloth current collector is large, so that the electrode active material is not only loaded on the surface of the nickel cloth, but also can occupy the inner gap of the nickel cloth, and the loading capacity of the electrode material on the current collector in unit area is increased; in addition, the electrode active material is fully contacted with the surface of the current collector, which is beneficial to fully contacting the electrode material with the conductive network and reducing the direct interface internal resistance of the electrode active material and the current collector in the electrode;
(5) the lithium ion battery and the super capacitor which are prepared by the nickel cloth current collector have small interface internal resistance, high energy density and high pseudo capacitance, and because the nickel cloth current collector has better processing performance compared with the traditional metal foil, the production efficiency of the lithium ion battery can be improved, the production cost is reduced, and the current collector substrate is made of a fabric (high polymer) material, can be automatically contracted and fused at high temperature, and improves the safety performance of the battery;
(6) the preparation method has simple process, easy operation and low cost, and is suitable for industrial large-scale production.
Drawings
Fig. 1 (a) and (b) are Scanning Electron Microscope (SEM) images of the nickel cloth current collector prepared in example 1 of the present invention, respectively;
FIG. 2 is a graph of the nickel cloth @ NiCo double metal hydroxide composite electrode of example 1 of the present invention at 50mV s-1Cyclic voltammograms at scan rate;
FIG. 3 shows a nickel cloth @ NiCo double metal hydroxide composite electrode of example 1 of the present invention at 5mA/cm2Constant current charge and discharge curve diagram under current density.
Detailed Description
The foregoing aspects of the present invention are described in further detail below by way of examples, but it should not be construed that the scope of the subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above aspects of the present invention are within the scope of the present invention.
Example 1
The preparation method of the nickel cloth current collector in the embodiment takes gauze as a substrate, and sequentially performs the processes of coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment on the substrate, so that the metal conductive nickel layer is uniformly coated on fibers of the substrate, and the method specifically comprises the following steps:
(1) roughening the substrate: soaking the substrate material in a roughening solution for 30min at 70 ℃, and then washing with deionized water to obtain a roughened substrate material, wherein the roughening solution is a sodium hydroxide aqueous solution, and the concentration of sodium hydroxide in the roughening solution is 200 g/L;
(2) sensitization and activation: soaking the roughened substrate material in the step (1) in a sensitizing and activating solution for 5min at room temperature, and then washing with deionized water to obtain the sensitized and activated substrate material, wherein the sensitizing and activating solution is a mixed solution composed of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid, the concentration of palladium chloride in the sensitizing and activating solution is 0.18g/L, the concentration of stannous chloride is 12g/L, the concentration of sodium chloride is 160g/L, and the concentration of hydrochloric acid is 10 ml/L;
the sensitization activation liquid is prepared by the following method:
(a) dissolving 0.18g of palladium chloride in 5ml of concentrated hydrochloric acid at room temperature to prepare a solution A;
(b) uniformly mixing 5ml of concentrated hydrochloric acid and 10ml of deionized water at room temperature to prepare a mixed solution, and dissolving 12g of stannous chloride in the mixed solution to prepare a solution B;
(c) respectively heating the solution A and the solution B to 70 ℃, keeping the temperature constant, and mixing the solution A and the solution B under the stirring condition to obtain a solution C;
(d) dissolving 160g of sodium chloride in 0.7L of deionized water to obtain a solution D, heating the solution D to 60 ℃, keeping the temperature constant, mixing the solution D and the solution C under the stirring condition, finally diluting to 1L to obtain a solution E, shaking uniformly, and filtering for later use;
(3) reduction: soaking the sensitized and activated substrate material in a reducing solution for 3min at room temperature, and then washing with deionized water to obtain the reduced substrate material, wherein the reducing solution is an aqueous solution of sodium hypophosphite, and the concentration of the sodium hypophosphite in the reducing solution is 30 g/L;
(4) chemical plating treatment: at room temperature, placing the reduced substrate material obtained in the step (3) in an electroless plating solution for reaction for 15min to plate a metal nickel layer on the surface of the substrate, wherein the electroless plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the electroless plating solution is 20g/L, the concentration of the trisodium citrate is 10g/L, the concentration of the sodium hypophosphite is 30g/L, and the concentration of the ammonium chloride is 30 g/L;
the chemical plating solution is prepared by the following method:
(i) respectively weighing 20g of nickel sulfate hexahydrate, 10g of trisodium citrate, 30g of sodium hypophosphite and 30g of ammonium chloride, uniformly dispersing the raw materials in 100mL of deionized water, and filtering to obtain a single-component concentrated solution;
(ii) adding the trisodium citrate concentrated solution prepared in the step (1) into a chemical plating bath, diluting, then sequentially adding an ammonium chloride concentrated solution, a nickel sulfate concentrated solution and a sodium hypophosphite concentrated solution under the stirring condition, uniformly stirring, diluting to 1L, and finally adjusting the pH value of the chemical plating bath to 8.5 by using a sodium hydroxide solution;
(5) and (3) post-treatment: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 120 ℃ for hydrothermal reaction for 8 hours, taking out the substrate material, washing and drying the substrate material by using deionized water and absolute ethyl alcohol to obtain the nickel cloth current collector, wherein the mixed solution consists of cobalt chloride, nickel chloride hexahydrate, HMT (hexamethylene tetramine) and deionized water, the cobalt chloride is 4mmol, the nickel chloride hexahydrate is 2mmol, the HMT (hexamethylene tetramine) is 10mmol, and the deionized water is 60 ml.
Fig. 1 (a) and (b) are Scanning Electron Microscope (SEM) images of the nickel cloth prepared in this embodiment, respectively, and it can be seen that a uniform layer of elemental nickel can be obtained on the surface of the gauze by this method, and the conductivity of the battery can be effectively improved.
The application performance is as follows:
the nickel cloth prepared by the embodiment is applied to a current collector to manufacture a lithium ion battery or a super capacitor, the electrochemical performance of the lithium ion battery or the super capacitor is performed in an electrochemical workstation, as shown in the figure, fig. 2 shows that the nickel cloth @ NiCo double metal hydroxide composite electrode is 50mV s-1The cyclic voltammetry curve under the scanning rate shows that the composite electrode has two pairs of redox peaks and provides efficient pseudocapacitance performance; FIG. 3 shows the nickel cloth @ NiCo double metal hydroxide composite electrode at 5mA/cm2Constant current charging and discharging curve under current density, and specific capacitance up to 0.4F cm-2。
Example 2
In the preparation method of the nickel cloth current collector, gauze is used as a substrate, and the substrate is subjected to coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment processes in sequence, so that the metal conductive nickel layer is uniformly coated on fibers of the substrate. The same process steps and process parameters as in example 1 were used in this example, except that the mixed solution in step (5) consisted of 6mmol of cobalt chloride, 10mmol of hexamethylenetetramine and 60ml of deionized water, and Hexamethylenetetramine (HMT) was used.
The nickel cloth prepared by the embodiment is tested by a Scanning Electron Microscope (SEM), the surface of the gauze substrate is plated with a layer of uniform metallic nickel simple substance, the conductivity of the battery can be effectively improved, and the electrochemical performance of the nickel cloth is tested to obtain the specific capacitance of about 0.28F cm-2。
Example 3
In the preparation method of the nickel cloth current collector, gauze is used as a substrate, and the substrate is subjected to coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment processes in sequence, so that the metal conductive nickel layer is uniformly coated on fibers of the substrate. The same process steps and process parameters as those in example 1 were used in this example, except that the mixed solution in step (5) of this example was composed of 6mmol of nickel chloride hexahydrate, 10mmol of hexamethylenetetramine and 60ml of deionized water, and Hexamethylenetetramine (HMT) and deionized water were used.
The nickel cloth prepared by the embodiment is tested by a Scanning Electron Microscope (SEM), the surface of the gauze substrate is plated with a layer of uniform metallic nickel simple substance, the conductivity of the battery can be effectively improved, and the electrochemical performance of the battery is tested to obtain the specific capacitance of about 0.33F cm-2。
Example 4
The preparation method of the nickel cloth current collector in the embodiment takes gauze as a substrate, and sequentially performs the processes of coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment on the substrate, so that the metal conductive nickel layer is uniformly coated on fibers of the substrate, and the method specifically comprises the following steps:
(1) roughening the substrate: soaking the substrate material in a roughening solution for 20min at 70 ℃, and then washing with deionized water to obtain a roughened substrate material, wherein the roughening solution is a sodium hydroxide aqueous solution, and the concentration of sodium hydroxide in the roughening solution is 150 g/L;
(2) sensitization and activation: soaking the roughened substrate material in the step (1) in a sensitizing and activating solution for 8min at room temperature, and then washing with deionized water to obtain the sensitized and activated substrate material, wherein the sensitizing and activating solution is a mixed solution composed of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid, and the concentration of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid in the sensitizing and activating solution is 0.15g/L, 10g/L, 150g/L and 5 ml/L;
the sensitization activation liquid is prepared by the following method:
(a) dissolving 0.15g of palladium chloride in 2.5ml of concentrated hydrochloric acid at room temperature to prepare a solution A;
(b) uniformly mixing 2.5ml of concentrated hydrochloric acid and 10ml of deionized water at room temperature to prepare a mixed solution, and dissolving 10g of stannous chloride in the mixed solution to prepare a solution B;
(c) respectively heating the solution A and the solution B to 70 ℃, keeping the temperature constant, and mixing the solution A and the solution B under the stirring condition to obtain a solution C;
(d) dissolving 150g of sodium chloride in 0.6L of deionized water to obtain a solution D, heating the solution D to 60 ℃, keeping the temperature constant, mixing the solution D and the solution C under the stirring condition, finally diluting to 1L to obtain a solution E, shaking uniformly, and filtering for later use;
(3) reduction: soaking the sensitized and activated substrate material in a reducing solution for 3min at room temperature, and then washing with deionized water to obtain the reduced substrate material, wherein the reducing solution is an aqueous solution of sodium hypophosphite, and the concentration of the sodium hypophosphite in the reducing solution is 25 g/L;
(4) chemical plating treatment: at room temperature, placing the reduced substrate material obtained in the step (3) in an electroless plating solution for reaction for 10min to plate a metal nickel layer on the surface of the substrate, wherein the electroless plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the electroless plating solution is 25g/L, the concentration of the trisodium citrate is 15g/L, the concentration of the sodium hypophosphite is 25g/L, and the concentration of the ammonium chloride is 25 g/L;
the chemical plating solution is prepared by the following method:
(i) respectively weighing 25g of nickel sulfate hexahydrate, 15g of trisodium citrate, 25g of sodium hypophosphite and 25g of ammonium chloride, uniformly dispersing the raw materials in 100mL of deionized water, and filtering to obtain a single-component concentrated solution;
(ii) adding the trisodium citrate concentrated solution prepared in the step (1) into a chemical plating bath, diluting, then sequentially adding an ammonium chloride concentrated solution, a nickel sulfate concentrated solution and a sodium hypophosphite concentrated solution under the stirring condition, uniformly stirring, diluting to 1L, and finally adjusting the pH value of the chemical plating bath to 9 by using a sodium hydroxide solution;
(5) and (3) post-treatment: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 120 ℃ for hydrothermal reaction for 8 hours, taking out the substrate material, washing and drying the substrate material by using deionized water and absolute ethyl alcohol to obtain the nickel cloth current collector, wherein the mixed solution consists of cobalt chloride, nickel chloride hexahydrate, HMT (hexamethylene tetramine) and deionized water, the cobalt chloride is 4mmol, the nickel chloride hexahydrate is 2mmol, the HMT (hexamethylene tetramine) is 10mmol, and the deionized water is 60 ml.
The nickel cloth prepared by the embodiment is tested by a Scanning Electron Microscope (SEM), the surface of the gauze substrate is plated with a layer of uniform metallic nickel simple substance, the conductivity of the battery can be effectively improved, and the electrochemical performance of the battery is tested to obtain the specific capacitance of about 0.35F cm-2。
Example 5
The preparation method of the nickel cloth current collector in the embodiment takes gauze as a substrate, and sequentially performs the processes of coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment on the substrate, so that the metal conductive nickel layer is uniformly coated on fibers of the substrate, and the method specifically comprises the following steps:
(1) roughening the substrate: soaking the substrate material in a roughening solution for 25min at 70 ℃, and then washing with deionized water to obtain a roughened substrate material, wherein the roughening solution is a sodium hydroxide aqueous solution, and the concentration of sodium hydroxide in the roughening solution is 180 g/L;
(2) sensitization and activation: soaking the roughened substrate material obtained in the step (1) in a sensitizing and activating solution for 10min at room temperature, and then washing with deionized water to obtain the sensitized and activated substrate material, wherein the sensitizing and activating solution is a mixed solution composed of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid, the concentration of palladium chloride in the sensitizing and activating solution is 0.2g/L, the concentration of stannous chloride is 15g/L, the concentration of sodium chloride is 170g/L, and the concentration of hydrochloric acid is 8 ml/L;
the sensitization activation liquid is prepared by the following method:
(a) dissolving 0.2g of palladium chloride in 4ml of concentrated hydrochloric acid at room temperature to prepare a solution A;
(b) uniformly mixing 4ml of concentrated hydrochloric acid and 10ml of deionized water at room temperature to prepare a mixed solution, and dissolving 15g of stannous chloride in the mixed solution to prepare a solution B;
(c) respectively heating the solution A and the solution B to 70 ℃, keeping the temperature constant, and mixing the solution A and the solution B under the stirring condition to obtain a solution C;
(d) dissolving 170g of sodium chloride in 0.8L of deionized water to obtain a solution D, heating the solution D to 60 ℃, keeping the temperature constant, mixing the solution D and the solution C under the stirring condition, finally diluting to 1L to obtain a solution E, shaking uniformly, and filtering for later use;
(3) reduction: soaking the sensitized and activated substrate material in a reducing solution for 3min at room temperature, and then washing with deionized water to obtain the reduced substrate material, wherein the reducing solution is an aqueous solution of sodium hypophosphite, and the concentration of the sodium hypophosphite in the reducing solution is 26 g/L;
(4) chemical plating treatment: at room temperature, placing the reduced substrate material obtained in the step (3) in an electroless plating solution for reaction for 20min to plate a metal nickel layer on the surface of the substrate, wherein the electroless plating solution is a mixed solution consisting of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the electroless plating solution is 26g/L, the concentration of the trisodium citrate is 12g/L, the concentration of the sodium hypophosphite is 28g/L, and the concentration of the ammonium chloride is 28 g/L;
the chemical plating solution is prepared by the following method:
(i) respectively weighing 26g of nickel sulfate hexahydrate, 12g of trisodium citrate, 28g of sodium hypophosphite and 28g of ammonium chloride, uniformly dispersing the raw materials in 100mL of deionized water, and filtering to obtain a single-component concentrated solution;
(ii) adding the trisodium citrate concentrated solution prepared in the step (1) into a chemical plating bath, diluting, then sequentially adding an ammonium chloride concentrated solution, a nickel sulfate concentrated solution and a sodium hypophosphite concentrated solution under the stirring condition, uniformly stirring, diluting to 1L, and finally adjusting the pH value of the chemical plating bath to 9.5 by using a sodium hydroxide solution;
(5) and (3) post-treatment: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at 120 ℃ for hydrothermal reaction for 8 hours, taking out the substrate material, washing and drying the substrate material by using deionized water and absolute ethyl alcohol to obtain the nickel cloth current collector, wherein the mixed solution consists of cobalt chloride, nickel chloride hexahydrate, HMT (hexamethylene tetramine) and deionized water, the cobalt chloride is 4mmol, the nickel chloride hexahydrate is 2mmol, the HMT (hexamethylene tetramine) is 10mmol, and the deionized water is 60 ml.
The nickel cloth prepared by the embodiment is tested by a Scanning Electron Microscope (SEM), the surface of the gauze substrate is plated with a layer of uniform metallic nickel simple substance, the conductivity of the battery can be effectively improved, and the electrochemical performance of the battery is tested to obtain the specific capacitance of about 0.38F cm-2。

Claims (10)

1. The preparation method of the nickel cloth current collector is characterized by comprising the following steps: the method is characterized in that gauze is used as a substrate, and the substrate is sequentially subjected to coarsening, sensitization and activation, reduction, chemical nickel plating and post-treatment processes, so that a metal conductive nickel layer is uniformly coated on fibers of the substrate, and the method specifically comprises the following steps:
(1) roughening the substrate: soaking the substrate material in a roughening solution for 20-30 min at 70 ℃, and then washing with deionized water to obtain a roughened substrate material, wherein the roughening solution is a sodium hydroxide aqueous solution, and the concentration of sodium hydroxide in the roughening solution is 150-200 g/L;
(2) sensitization and activation: soaking the roughened substrate material in the step (1) in a sensitizing and activating solution for 5-10 min at room temperature, and then washing with deionized water to obtain the sensitized and activated substrate material, wherein the sensitizing and activating solution is a mixed solution composed of palladium chloride, stannous chloride, sodium chloride and hydrochloric acid, and the concentration of palladium chloride in the sensitizing and activating solution is 0.15-0.2 g/L, the concentration of stannous chloride is 10-15 g/L, the concentration of sodium chloride is 150-170 g/L, and the concentration of hydrochloric acid is 5-10 ml/L;
(3) reduction: soaking the sensitized and activated substrate material in a reducing solution for 2-5 min at room temperature, and then washing with deionized water to obtain the reduced substrate material, wherein the reducing solution is an aqueous solution of sodium hypophosphite, and the concentration of the sodium hypophosphite in the reducing solution is 25-30 g/L;
(4) chemical nickel plating: at room temperature, placing the reduced substrate material obtained in the step (3) in an electroless plating solution for reaction for 10-20 min to plate a metal nickel layer on the surface of the substrate, wherein the electroless plating solution is a mixed solution composed of nickel sulfate hexahydrate, trisodium citrate, sodium hypophosphite and ammonium chloride, the concentration of the nickel sulfate hexahydrate in the electroless plating solution is 20-25 g/L, the concentration of the trisodium citrate is 10-15 g/L, the concentration of the sodium hypophosphite is 25-30 g/L, the concentration of the ammonium chloride is 25-30 g/L, and the pH value of the electroless plating solution is 8.5-9.5;
(5) and (3) post-treatment: and (3) placing the substrate material plated with the metallic nickel layer on the surface, which is prepared in the step (4), in a mixed solution at the temperature of 120 ℃ for hydrothermal reaction for 8 hours, taking out the substrate material, washing and drying the substrate material by using deionized water and absolute ethyl alcohol to obtain the nickel cloth current collector, wherein the mixed solution consists of cobalt chloride and/or nickel chloride hexahydrate, hexamethylenetetramine and deionized water, and the molar ratio of the cobalt chloride and/or nickel chloride hexahydrate to the hexamethylenetetramine is 3: 5, the molar volume ratio of the hexamethylene tetramine to the deionized water is 1 mmol: 6 mL.
2. The method for preparing a nickel cloth current collector as claimed in claim 1, wherein: the gauze is pure cotton absorbent gauze.
3. The method for preparing a nickel cloth current collector as claimed in claim 1 or 2, wherein: the soaking time in the step (2) is 5min, and the chemical nickel plating time in the step (4) is 15 min.
4. The method for preparing a nickel cloth current collector as claimed in claim 1 or 2, wherein: the concentration of palladium chloride in the sensitization activation liquid in the step (2) is 0.18g/L, the concentration of stannous chloride is 12g/L, the concentration of sodium chloride is 160g/L, and the concentration of hydrochloric acid is 10 ml/L.
5. The method for preparing a nickel cloth current collector as claimed in claim 1 or 2, wherein: the mixed solution in the step (5) is composed of cobalt chloride, nickel chloride hexahydrate, hexamethylenetetramine and deionized water, wherein the molar ratio of the cobalt chloride to the nickel chloride hexahydrate to the hexamethylenetetramine is 2: 1: 5.
6. the method for preparing a nickel cloth current collector as claimed in claim 1 or 2, wherein: the sensitization activation liquid in the step (2) is prepared by the following method:
(a) at room temperature, dissolving palladium chloride in a small amount of concentrated hydrochloric acid according to a ratio to prepare a solution A;
(b) preparing mixed solution from concentrated hydrochloric acid and deionized water according to the volume ratio of 1:2 at room temperature, and dissolving stannous chloride in the mixed solution according to the proportion to prepare solution B;
(c) respectively heating the solution A and the solution B to 70 ℃, keeping the temperature constant, and mixing the solution A and the solution B under the stirring condition to obtain a solution C;
(d) dissolving sodium chloride in deionized water according to a ratio to prepare a solution D, heating the solution D to 60 ℃, keeping the temperature constant, mixing the solution D and the solution C under a stirring condition to obtain a solution E, diluting the solution E to a specified volume, shaking up, and filtering for later use.
7. The method for preparing a nickel cloth current collector as claimed in claim 1 or 2, wherein: and (4) the concentration of nickel sulfate hexahydrate in the chemical plating solution is 20g/L, the concentration of trisodium citrate is 10g/L, the concentration of sodium hypophosphite is 30g/L, and the concentration of ammonium chloride is 30 g/L.
8. A composite electrode, characterized by: comprising a nickel cloth current collector obtained by the method of claim 1 or 2.
9. A flexible lithium ion battery, characterized in that: the battery comprising the composite electrode according to claim 8 as a positive electrode material.
10. A flexible supercapacitor, characterized by: the capacitor containing the composite electrode of claim 8.
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