CN1116706C - Surficially roughened foam nickel and its preparing process - Google Patents

Surficially roughened foam nickel and its preparing process Download PDF

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Publication number
CN1116706C
CN1116706C CN99115542A CN99115542A CN1116706C CN 1116706 C CN1116706 C CN 1116706C CN 99115542 A CN99115542 A CN 99115542A CN 99115542 A CN99115542 A CN 99115542A CN 1116706 C CN1116706 C CN 1116706C
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nickel
resin paint
foam nickel
electroplating
anode
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CN1249541A (en
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钟发平
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The present invention relates to a surface roughening foam nickel and a new preparation process thereof, which is characterized by spraying uniform lattice type attachments on the surface of base material at the arbitrarily stages of electroplating processes before or after the metallization of sponge matrix. The surface roughening foam nickel prepared by adopting the present invention not only can reduce the content of adhesives in battery pole pieces, but also can enhance the intensity of the battery pole pieces, increase the life time and the capacity of batteries, and greatly increase the technical performance of the batteries, and thus, the surface roughening foam nickel is a novel material for high energy batteries.

Description

Process for producing foamed nickel with roughened surface
Technical Field
The invention relates to a production process of foamed nickel in the field of high-energy battery materials.
Background
The traditional production process of the foam nickel, such as the production process of the blocky and continuous strip foam nickel, comprises the following steps: conducting treatment of the sponge matrix, electroplating until a certain surface density is reached, and finally burning, decarbonizing, reducing, annealing and cooling (hereinafter referred to as heat treatment). The conductive treatment generally has three modes, namely coating conductive adhesive, chemical nickel plating and vacuum ion sputtering nickel. The block-shaped continuous strip-shaped foamed nickel produced by the traditional process is observed to be in a surface smooth type under a microscope with enough magnification, the binding force between the battery plate forming slurry prepared by mixing, stirring and slurrying the components such as the electrode active material, the adhesive, the solvent and the like according to a certain proportion and the smooth surface is poor, when the battery is charged and discharged for many times, the volume of the electrode active material is also continuously expanded and contracted along with the charging and discharging processes, so that the electrode active material falls off from the surface of the foamed nickel base material after the charging and discharging processes for many times, and the service life of the battery is influenced. On the other hand, the smooth surface needs enough adhesive to have enough binding force, so that the electrode using the smooth surface foamed nickel as the base material needs enough adhesive to maintain the strength of the battery pole piece and ensure the battery life of the battery after multiple charging and discharging, but in the pole piece with the same volume, the increase of the adhesive dosage inevitably leads to the reduction of the active material dosage, and the reduction of the active material dosage can sacrifice the capacity of the battery.
Disclosure of Invention
The invention aims to provide the foam nickel and the production process thereof, wherein the foam nickel not only can reduce the content of an adhesive in a battery pole piece, but also can enhance the strength of the battery pole piece, increase the capacity and the service life of the battery and greatly improve the technical performance of the battery.
The technical solution of the invention is as follows: before the traditional sponge matrix for producing the foamed nickel is subjected to the conductive treatment or in the subsequent electroplating stage, a layer of attachments distributed in a uniform lattice shape is sprayed on the surface of the base material, wherein the attachments are coatings with strong adhesive force with the sponge matrix, and the coatings comprise epoxy resin coatings, alkyd resin coatings, acrylic resin coatings, vinyl resin coatings, polyurethane resin coatings, organic silicon resin coatings, amino resin coatings or binary and ternary mixed coatings of the coatings.
The technical scheme is characterized in that the specific process is one of the following two modes:
1. the sponge base body is sprayed with a layer of attachment coating which is distributed in a uniform lattice shape, after the sponge base body is dried and formed, any one of conductive treatment of coating conductive adhesive, chemical nickel plating or vacuum ion sputtering nickel is carried out, then electroplating is carried out, and finally the finished product of the invention is prepared by a heat treatment process.
2. After the sponge matrix is treated by conductive treatment of coating conductive adhesive or chemical nickel plating or vacuum ion sputtering nickel, a layer of attachment coating distributed in a uniform lattice shape is sprayed on the surface of the base material in the subsequent electroplating stage, the sprayed semi-finished product of the foam nickel is subjected to anode dissolution, namely, the anode and the cathode of the electroplating bath are reversely connected, so that the semi-finished product of the foam nickel becomes the anode, the original anode is changed into the cathode, and finally, the subsequent heat treatment process is carried out to prepare the finished product of the foam nickel.
The anodic dissolution process is briefly described as follows:
1. reversely connecting the positive electrode and the negative electrode of the electroplating bath to make the semi-finished product of the foamed nickel be an anode and change the original anode into a cathode;
2. the electroplating solution adopts a traditional watt electroplating solution or nickel sulfamate electroplating solution system, and the PH value, the electroplating temperature and the like adopt the existing mature technology;
3. the anode dissolution current is controlled to be 10-5000A/m2；
4. The dissolution time of the anode was controlled within 1 hour.
Through the anode dissolving process, the part with the attached matter can not be dissolved, but the foam nickel part without the attached matter is dissolved, and through controlling the current and time and the spraying process parameters described in the embodiment 1, foam nickel semi-finished products with different roughening shapes and different roughness surfaces can be obtained, and then the finished product of the invention is prepared through the subsequent heat treatment process.
The technical scheme of the invention makes the surface of the blocky or continuous strip-shaped foam nickel uniformly roughened, the surface of the foam nickel is in a rough structure under an optical microscope with enough magnification, the microcosmic rough surface type foam nickel obtained by adopting the process of the invention has basic technical performance completely reaching the international advanced technical index of the existing foam nickel, and the battery using the foam nickel has great advantages in greatly improving the technical performance such as capacity, service life and the like.
The specific experimental data and detection results of the invention are as follows:
a comparative experiment is carried out on the AA type nickel-hydrogen battery produced by adopting the foam nickel AAI obtained by the traditional process and the foam nickel AAII with rough surface obtained by the process of the invention: the positive electrode material adopts spherical nickel hydroxide, cobaltous oxide, nickel powder and sodium carboxymethyl cellulose, and adopts two different foam nickel AAI and AAII respectively; the negative electrode material adopts hydrogen storage alloy powder, nickel powder, sodium carboxymethylcellulose, polytetrafluoroethylene and two different kinds of foam nickel AAI and AAII respectively. Therefore, the materials selected above are all the same except for the foamed nickel, and the mixture ratio and the process are all the same, and the average performance of the 50 AA type nickel-hydrogen batteries produced under the condition is as follows: performance batteries produced using AAI battery capacity (mAh) 13001450 times of life (1C, 100% DOD) 450550 operating platform voltage (1C) 1.201.22 internal resistance (m Ω) 2618 notes produced using AAII: DOD in the table above refers to depth of discharge.
As can be seen from the above table, the nickel-metal hydride battery produced by using the rough-surface nickel foam of the present invention has greater advantages in terms of battery capacity, battery life, battery internal resistance, and platform operating voltage than the nickel-metal hydride battery produced by using the conventional nickel foam.
The performance test comparison results of the rough surface foam nickel AAII and the traditionalfoam nickel AAI are shown in the following table: performance AAI AAII porosity% 96.5% 96%Longitudinal tensile strength N/cm2189191 transverse tensile strength N/cm2126125 percent elongation in longitudinal direction 88 percent elongation in transverse direction 1616.5 percent areal density g 500 + -30500 + -30 softness qualification nickel Ni ppm with the balance being Fe 105100 carbon C110100 copper Cu 48.557 silicon Si 2535 sulfur S6860
As can be seen from the above table, the performance index of the surface-roughened nickel foam produced by the process of the present invention is completely consistent with the current international advanced performance index of the traditional nickel foam.
Detailed Description
Example 1: the invention sprays a layer of attachments distributed in a uniform lattice shape on the sponge matrix for traditional foam nickel production, such as a polyurethane sponge matrix, and the attachments are coatings with stronger adhesive force with the sponge matrix, and comprise epoxy resin coatings, alkyd resin coatings, acrylic resin coatings, ethylene resin coatings, polyurethane resin coatings, organic silicon resin coatings, amino resin coatings or binary and ternary mixed coatings of the coatings. The spraying method for spraying the attachments on the sponge matrix can adopt the prior art of air spraying or airless sprayingCoating or electrostatic spraying: air spraying is a coating mode that the air flow of compressed air is used for atomizing coating into fog and coating the surface of an object to be coated under the driving of the air flow, a set of complete air spraying device comprises an air compressor, an air conveying pipe, an air oil-water separator, an air storage tank, a spray gun, a coating tank, a spraying room and the like, and the construction key points of the air spraying are as follows: 1. the atomization condition should be satisfied do = ( 3.6 × 10 5 Q 1 ) 0.75 Do-average particle diameter of the coating after atomization, Q1-air usage/paint ejection; 2. spraying distance; 3. the moving speed of the spray gun; 4. overlapping the spray patterns; 5. the viscosity of the coating is generally suitably as follows: nitrolacquer and thermoplastic solvent lacquer: 16-18 seconds, thermosetting solvent coating (amino, acrylic): 18-25 seconds, self-drying alkyd and polyurethane coatings: 25-30 seconds; 6. care should be taken to clean the equipment and the environment. The airless spraying is a new technology of coating, which is to press and send the coating by means of a high-pressure pump in a closed container, the speed of the high-pressure coating sprayed from a small hole is very high, the volume of the coating expands suddenly with the sudden drop of impact air and pressure, the solvent volatilizes quickly to disperse and atomize, and flies to the coated object at high speed. The electrostatic spraying is also called high-frequency electrostatic spraying, which utilizes the basic principle of static electricity to charge the coating in an electric field and is absorbed on a workpiece with opposite charges under the action of the force of the electric field to complete the coating process, and the process comprises the following steps: high voltage negative electricity is firstly applied to electrode with sharp edge or pointed end, the workpiece is grounded, so that an unevenelectrostatic field is formed between negative electrode and workpiece, and by means of corona phenomenon, firstly near negative electrodeExciting a large amount of dissociated electrons, atomizing the paint primarily by high-pressure air or centrifugal power, introducing the atomized paint into an electric field, combining paint particles and electrons into negative particles, further atomizing under the action of the electric field force, moving to a different electrode (workpiece), and finally depositing on the workpiece. After a layer of attachments in a uniform lattice shape is sprayed on the sponge matrix, the sponge matrix is dried and formed, and then is subjected to conductive treatment and electroplating treatment. The drying adopts natural drying or hot air drying, the conductive treatment and the electroplating treatment are both the prior art, the conductive treatment modes are three, one of the conductive treatment modes can be adopted at will, and the three conductive treatment modes are as follows: coating conductive adhesive, chemical nickel plating and vacuum ion sputtering nickel. Chemical nickel plating in the prior art: is that the sponge is subjected to rough treatmentActivation, activation and chemical plating, so that a very thin layer of nickel-phosphorus alloy is deposited on the sponge, and the sponge has good conductive capability. Vacuum ion sputtering nickel of the prior art: the method is characterized in that sputtered metallic nickel is deposited on the sponge by a metallic nickel target under the magnetic control condition in a vacuum environment. Depositing a layer of metallic nickel film on the sponge, coating conductive adhesive in the prior art: the sponge is prepared by adding conductive powder such as conductive powdered carbon into a solvent, mixing into slurry, uniformly coating the slurry on the sponge, and drying to obtain the sponge with good conductive capability. The conductive treatment of this example 1, i.e., one of the three optional ways,is merely to replace the sponge with a sponge substrate on which a layer of attachments is sprayed in a uniform lattice pattern. The sponge matrix with good conductivity after the conductive treatment is subjected to subsequent electroplating treatment to ensure that the nickel content on the sponge matrix reaches a certain specified value, usually at 300-2Electroplating is a basic process (nickel plating is taken as an example) of immersing a sponge substrate subjected to conductive treatment in a metal salt (such as NiSO)4) The solution is used as a cathode, the metal nickel plate is used as an anode, and after a direct current power supply is switched on, a metal nickel coating is deposited on a substrate, for example, when nickel is plated in a nickel sulfate electroplating solution, a reaction that nickel ions are obtained on the cathode to reduce electrons into nickel metal is carried out, which is a main reactionThe reaction formula is as follows: the electroplating solution adopts a classical watt electroplating system or a nickel sulfamate system, the electroplating temperature ranges from 30 ℃ to 70 ℃, the pH value ranges from 2 to 7, and the continuous electroplating time is determined according to the requirements of users on the surface density and is generally between 0.2 and 8 hours. The semi-finished product after the nickel plating amount reaches the specified value needs to be subjected to a heat treatment stage, the heat treatment is also the prior art, and a block-shaped or continuous strip-shaped foam nickel finished product with a roughened surface can be obtained after the heat treatment of five procedures of sponge burning, decarburization, reduction, annealing and cooling, wherein the sintering temperature range is generally between 200 ℃ and 1300 ℃.
Example 2: after the sponge matrix is subjected to conductive treatment, nickel is electroplated, after the nickel amount reaches a certain value, attachments in a uniform lattice shape are sprayed, the attachments can be selected from the coating described in the embodiment 1, after a layer of attachments distributed in a uniform lattice shape is sprayed, anode dissolution is carried out, the foam nickel without the attachments is gradually dissolved along with the prolonging of the electroplating time, the dissolution amount of the nickel can be controlled through the anode dissolution time, and the nickel covered by the attachments cannot be dissolved, so that the foam nickel semi-finished products with different roughened shapes and rough surfaces can be obtained by effectively adjusting the anode dissolution time, the current magnitude and the spraying process parameters. The semi-finished product with the nickel reaching the specified value after the electroplating treatment is subjected to five processes of sponge burning, decarburization, reduction, annealing and cooling to finally obtain the blocky or continuous strip-shaped foamed nickel with rough surface.
The anodic dissolution process is briefly described as follows:
1. reversely connecting the positive electrode and the negative electrode of the electroplating bath to make the semi-finished product of the foamed nickel be an anode and change the original anode into a cathode;
2. the electroplating solution adopts a traditional watt electroplating solution or nickel sulfamate electroplating solution system, and the PH value, the electroplating temperature and the like adopt the existing mature technology;
3. the anode dissolution current is controlled to be 10-5000A/m2；
4. The anodic dissolution time was controlled within 1 hour.
Through the anode dissolving process, the part with attached attachments can not be dissolved, but the foam nickel part without attached attachments is dissolved, and the foam nickel semi-finished products with different roughened shapes and different roughness surfaces can be obtained by controlling the current and the time and the spraying process parameters, and then the finished product of the invention is prepared through the subsequent heat treatment process.

Claims (2)

1. A process for preparing the foam nickel with roughened surface features that before the sponge matrix for preparing the foam nickel is treated by electric conduction or electroplating, a layer of adhesive is sprayed on the surface of said sponge matrix, which has stronger adhesive force to the sponge matrix, including epoxy resin paint, alkyd resin paint, acrylic resin paint, vinyl resin paint, polyurethane resin paint, organosilicon resin paint, amino resin paint, etc.
2. The process according to claim 1, wherein the step of coating the surface of the substrate with the coating material is further performed by anodic dissolution, wherein the anodic dissolution comprises:
a. reversely connecting the positive electrode and the negative electrode of the electroplating bath to make the semi-finished product of the foamed nickel be an anode and change the original anode into a cathode;
b. the electroplating solution adopts watt electroplating solution or nickel sulfamate electroplating solution system;
c. the anode dissolution current is controlled to be 10-5000A/m2；
d. The anodic dissolution time was controlled within 1 hour.
CN99115542A 1999-08-27 1999-08-27 Surficially roughened foam nickel and its preparing process Expired - Lifetime CN1116706C (en)

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Application Number Priority Date Filing Date Title
CN99115542A CN1116706C (en) 1999-08-27 1999-08-27 Surficially roughened foam nickel and its preparing process

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Application Number Priority Date Filing Date Title
CN99115542A CN1116706C (en) 1999-08-27 1999-08-27 Surficially roughened foam nickel and its preparing process

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CN1116706C true CN1116706C (en) 2003-07-30

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Publication number Priority date Publication date Assignee Title
CN100360225C (en) * 2005-11-11 2008-01-09 中山大学 Platinum carried foamed nickel catalytic material, its preparation method and application
CN104868134B (en) * 2015-04-17 2017-04-19 华南理工大学 Foam metal-carbon nanotube composite material, and preparation method and application thereof
CN105568268A (en) * 2015-12-18 2016-05-11 有研粉末新材料（北京）有限公司 Sponge substrate chemical nickeling device
CN109309193A (en) * 2018-09-13 2019-02-05 深圳光韵达机电设备有限公司 The lithium ion cell electrode structure and its processing method of high-specific surface area and application
CN113328103B (en) * 2021-05-13 2022-03-25 深圳先进储能材料国家工程研究中心有限公司 Preparation method of base material for gas diffusion layer of fuel cell

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