CN110923769B - Electroplating method of thin lead coating of carbon grid of lead-carbon battery - Google Patents

Electroplating method of thin lead coating of carbon grid of lead-carbon battery Download PDF

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CN110923769B
CN110923769B CN201911002574.1A CN201911002574A CN110923769B CN 110923769 B CN110923769 B CN 110923769B CN 201911002574 A CN201911002574 A CN 201911002574A CN 110923769 B CN110923769 B CN 110923769B
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carbon
grid
lead
carrying
battery
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CN110923769A (en
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邵勤思
张树祥
傅倩如
臧银亮
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Zhaoqing Leoch Battery Technology Co Ltd
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Zhaoqing Leoch Battery Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/34—Electroplating: Baths therefor from solutions of lead
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/16—Electroplating with layers of varying thickness
    • 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
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • 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
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • 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
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
    • H01M4/84—Multi-step processes for manufacturing carriers for lead-acid accumulators involving casting
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

An electroplating method of a thin lead coating of a carbon grid of a lead-carbon battery comprises the following steps: filling the mixed carbon slurry into a forming mold to obtain a carbon grid; sequentially carrying out oil removal operation on the carbon plate grids; carrying out high-temperature baking operation on the carbon plate grid; sequentially carrying out coarsening operation on the carbon plate grid; by SnCl2Sensitizing the carbon plate grid by the solution; using PdCl2Activating the carbon plate grid by the solution; placing the carbon plate grid in copper plating solution, and carrying out copper plating operation to form a substrate copper layer on the surface of the carbon plate grid; the carbon grid is placed in a lead plating solution and a lead plating operation is performed to form a thin lead plating layer on the surface of the copper layer of the substrate. The substrate copper layer not only has better adhesive capacity with the surface of carbon grid, and its bonding ability with electroplating lead layer is also stronger, can form electroplating lead layer on the surface of carbon grid, and then can make carbon grid and tin cream affinity higher, through the cladding of copper cladding and lead cladding to carbon grid, carbon grid mechanical properties is more outstanding.

Description

Electroplating method of thin lead coating of carbon grid of lead-carbon battery
Technical Field
The invention relates to the technical field of lead-carbon batteries, in particular to an electroplating method of a thin lead coating of a carbon grid of a lead-carbon battery.
Background
At present, the electrodes of lead-acid batteries are mainly made of lead and its oxides, and the electrolyte is a sulfuric acid solution. Since 1859 the lead-acid storage battery invented by frant of french americans, the lead-acid battery has undergone more than 150 years of development process, the lead-acid battery has low cost, long service life and good safety performance, and the recovery rate of the waste battery is as high as more than 95%, so the lead-acid battery is always the most widely used product in the battery field.
With the rapid development of electric automobiles and electric bicycles, a novel storage battery based on a lead-carbon technology, namely a lead-carbon battery, is gradually developed, activated carbon is added into lead paste of a negative electrode of the lead-acid battery to serve as a buffer material, and the carbon material is a high-quality material for storing, retaining and releasing static charges and can instantly gather and store a large amount of charges, so that the battery has higher power density, can finish charging in shorter time, can work under high multiplying power and better meets the development requirements of electric vehicles.
The lead-carbon battery negative electrode grid is prepared by pressing and sintering a plurality of materials such as graphite, silicon, titanium, cellulose and the like, lead paste is arranged in the negative electrode carbon grid, and the main material of the lead-carbon battery negative electrode grid is graphite.
Furthermore, the surface of the traditional carbon grid is the main carbon element, and when the tin paste is filled in the carbon grid, the affinity between the tin paste and the surface of the carbon grid is far lower than that between the tin paste and the lead grid or the lead alloy grid, so that the electrical performance of the lead-carbon battery is reduced.
Disclosure of Invention
Therefore, the electroplating method of the thin lead plating layer of the carbon grid of the lead-carbon battery, which can enable the carbon grid to have good mechanical performance and enable the carbon grid to have high affinity with tin paste, is needed to be provided.
An electroplating method of a thin lead coating of a carbon grid of a lead-carbon battery comprises the following steps:
s110: mixing and stirring a carbon raw material and a binder to obtain mixed carbon slurry;
s120: filling the mixed carbon slurry into a forming die, and performing extrusion forming to obtain a carbon grid;
s130: sequentially carrying out oil removal operation and water washing operation on the carbon grid;
s140: carrying out high-temperature baking operation on the carbon plate grid;
s150: carrying out coarsening operation and washing operation on the carbon grid in sequence;
s160: by SnCl2Sensitizing the carbon grid by using the solution, and then washing;
s170: using PdCl2Activating the carbon grid by using the solution, and then washing the carbon grid by using water;
s180: placing the carbon plate grid in copper plating solution, carrying out copper plating operation to form a substrate copper layer on the surface of the carbon plate grid, and then carrying out washing operation, wherein the thickness of the substrate copper layer is 2-5 microns;
s190: and placing the carbon plate grid in a lead plating solution, carrying out lead plating operation to form a thin lead plating layer on the surface of the substrate copper layer, and then carrying out water washing operation, wherein the thickness of the thin lead plating layer is 6-15 microns.
In one embodiment, the carbon feedstock is at least one of flygraphite, all-carbon aerogel, carbon foam, conductive graphite, carbon black, and acetylene black.
In one embodiment, the carbon raw material is mixed and stirred in advance with an aqueous ethanol solution before being mixed and stirred with the binder.
In one embodiment, after the lead plating operation and the water washing operation are sequentially performed, a vacuum drying operation is further performed on the carbon plate grid by using a vacuum drying device.
In one embodiment, the high-temperature baking operation is performed by using an oven at a temperature of 550-600 ℃, and the high-temperature gas in the oven is continuously pumped out while the dry inert gas is supplemented into the oven.
In one embodiment, the roughening operation is performed by immersing the carbon plate grid into the roughening solution at a temperature of 85-100 ℃.
In one embodiment, the copper plating solution comprises a copper salt, a complexing agent, a reducing agent, an accelerator and an inhibitor.
In one embodiment, the carbon grid is filled with solder paste that adheres to the thin lead plating.
According to the electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery, the substrate copper layer is formed on the carbon grid in advance, on one hand, the conductive capacity of copper metal is quite excellent, the conductive capacity can be improved, the conductive capacity of the carbon grid cannot be influenced, and on the other hand, the current passing capacity of the carbon grid can be improved.
Drawings
Fig. 1 is a flow chart illustrating steps of a method for electroplating thin lead coatings on a carbon grid of a lead-carbon battery according to an embodiment.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
As shown in fig. 1, the electroplating method of the thin lead plating layer of the carbon grid of the lead-carbon battery in one embodiment comprises the following steps:
s110: and mixing and stirring the carbon raw material and the binder to obtain mixed carbon slurry.
Through the step S110, a viscous mixed carbon slurry can be prepared so as to be filled in a grid forming mold for extrusion forming operation.
In order to effectively reduce the overall weight of the carbon grid and ensure the mechanical properties of the carbon grid, preferably, the carbon raw material is at least one of flight graphite, all-carbon aerogel, carbon foam, conductive graphite, carbon black and acetylene black; further, the carbon raw material comprises flight graphite, all-carbon aerogel, foam carbon, conductive graphite, carbon black and acetylene black; furthermore, the mass ratio of the flying graphite to the all-carbon aerogel to the foam carbon to the conductive graphite to the carbon black to the acetylene black is (4-20): (5-20): (20-70): (2-5): (1-3): (0.2-0.3), the carbon raw materials in the proportion can effectively reduce the overall weight of the carbon grid, and the mechanical property of the carbon grid can be ensured to be about half of the weight of a common alloy grid.
Preferably, the binder is at least one of polytetrafluoroethylene, carboxymethyl cellulose and neoprene, and further, the binder includes polytetrafluoroethylene, carboxymethyl cellulose and neoprene.
Preferably, the carbon raw material is also mixed and stirred in advance with an aqueous ethanol solution before being mixed and stirred with the binder.
S120: and filling the mixed carbon slurry into a forming die, and performing extrusion forming to obtain the carbon grid.
After the mixed carbon slurry is filled in a forming die, a carbon grid can be obtained through an extrusion operation, for example, through a high-temperature extrusion operation.
Preferably, after the extrusion molding operation, the forming mold and the carbon plate grid are dried and decontaminated together at 130-200 ℃ to remove water and organic solvent.
In order to reduce the deformation degree of the carbon grid and make the metallographic structure of the carbon grid more uniform and compact, preferably, after the drying and impurity removing operation, the carbon grid is subjected to normal-temperature extrusion shaping operation under the pressure condition of 300-350 kpa; heating the carbon grid to 160-180 ℃ under the pressure condition of 300-350 kpa to perform high-temperature extrusion shaping operation on the carbon grid; therefore, the normal-temperature extrusion shaping operation, namely the primary prepressing operation, is carried out on the carbon grid under the pressure condition of 300-350 kpa, so that the large gap or large hole caused by the reasons of die forming or raw materials per se can be improved under the mild pressure and temperature, the overall porosity of the carbon grid is better, and the problem of uneven local compaction effect caused by direct high-temperature extrusion shaping is avoided. The deformation degree can be reduced, so that the grid metallographic structure is more uniform and compact; further, the normal-temperature extrusion shaping operation is combined, so that after the overall porosity of the carbon grid reaches a better level, the high-temperature extrusion shaping operation is performed, the plasticity of the carbon grid is changed through temperature, namely, at least the feasible denaturation and the exhaust performance are improved, the compactness of the carbon grid is further improved, irregular gaps or holes can be effectively eliminated, the bonding performance among carbon raw materials is improved, and the electrical conductivity of the carbon grid is better.
S130: and sequentially carrying out oil removal operation and water washing operation on the carbon grid.
It is understood that since the carbon grid is formed by die extrusion, which involves a demolding process and the like, an oil molding such as a mold release agent and the like is inevitably introduced, and therefore, a degreasing operation is necessary, preferably, a degreasing operation is performed using an alkali solution, or a degreasing operation is performed using a water-soluble organic solvent.
Preferably, before the degreasing operation is performed on the carbon grid, a pressing and shaping operation is also performed on the carbon grid.
S140: and carrying out high-temperature baking operation on the carbon grid.
By carrying out high-temperature baking operation on the carbon grid, residual moisture and organic matters on the carbon grid can be effectively removed.
Preferably, the high-temperature baking operation is performed by using an oven at a temperature of 550-600 ℃, high-temperature gas in the oven is continuously pumped away, and dry inert gas is supplemented into the oven, so that residual moisture and organic matters on the carbon grid are better removed.
S150: and sequentially carrying out coarsening operation and washing operation on the carbon grid.
The coarsening operation is carried out on the carbon grid to increase the roughness, so that the effective surface area of the surface of the carbon grid can be increased, and the adhesion capability to a substrate copper layer is improved.
It should be noted that, because the surface of the carbon grid has more or less impurities, especially the carbon grid is made of carbon and is extruded through a die, and the surface of the carbon grid is rougher compared with the hardware or plastic, that is, the surface of the carbon grid is more hollow and has stronger dirt-collecting and dirt-holding capacity than the hardware or plastic, and the impurities attached to the surface of the carbon grid, such as dust or solid oil dirt, have a great influence on the adhesion of the copper layer of the substrate, it is necessary to clean the impurities, preferably, after step S150 and before step S160, the carbon grid is further subjected to a high-pressure spray cleaning operation with a cleaning solution to remove the impurities in deep gaps or cavities on the surface of the carbon grid, so as to improve the adhesion of the copper layer to the substrate, because the carbon grid has hard and brittle properties, operators need to flexibly adjust the water pressure and the spray rinsing time according to the material and the thickness of the carbon grid.
Preferably, under the temperature condition of 85-100 ℃, the carbon plate grid is immersed in the roughening solution to carry out roughening operation; preferably, a physical grinding mode is adopted to carry out the roughening operation.
S160: by SnCl2Sensitizing the carbon grid by using the solution, and then washing.
S170: using PdCl2And (3) activating the carbon grid by using the solution, and then, washing the carbon grid by using water.
By using SnCl beforehand2(stannous chloride) solution pairThe carbon grid is sensitized and Sn can be attached to the surface of the carbon grid2+Ions, in turn in PdCl2Activating in a (palladium dichloride) solution to form palladium metal particles with catalytic action on the surface of the carbon grid so as to better perform the copper electroplating operation of a substrate copper layer.
S180: and placing the carbon plate grid in a copper plating solution, carrying out copper plating operation to form a substrate copper layer on the surface of the carbon plate grid, and then carrying out water washing operation.
Through carrying out sensitization operation and activation operation on the carbon grid, a substrate copper layer can be formed during the copper electroplating operation, and the adhesion between the substrate copper layer and the surface of the carbon grid is better.
Preferably, the copper plating solution comprises copper salt, complexing agent, reducing agent, promoter and inhibitor; further, the copper salt is copper sulfate, copper chloride or copper nitrate; the complexing agent is potassium sodium tartrate, sodium citrate, ethylene diamine tetraacetic acid disodium or triethanolamine; the reducing agent is formaldehyde, glyoxal, glyoxylic acid or hypophosphite; the accelerant is sodium polydithio-dipropyl sulfonate or 3-mercapto-1-propane sodium sulfonate; the inhibitor is polyethylene glycol.
S190: and placing the carbon plate grid in a lead plating solution, carrying out lead plating operation to form a thin lead plating layer on the surface of the substrate copper layer, and then carrying out water washing operation.
It should be noted that, as proved by multiple experiments of the inventor, the adhesion degree of the carbon grid is very poor and the problem of peeling and loosening is easily caused when the lead is directly electroplated on the surface of the carbon grid.
According to the electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery, the substrate copper layer is formed on the carbon grid in advance, on one hand, the conductive capacity of copper metal is quite excellent, the conductive capacity can be improved, the conductive capacity of the carbon grid cannot be influenced, and on the other hand, the current passing capacity of the carbon grid can be improved.
Preferably, after the lead plating operation and the water washing operation are sequentially performed, a vacuum drying operation is further performed on the carbon plate grid by using a vacuum drying device.
Preferably, the thickness of the substrate copper layer is 2-5 microns; the thickness of the thin lead plating layer is 6 micrometers to 15 micrometers, and it should be particularly noted that, because the lead plating layer is used to avoid the problem of reduced affinity caused by direct contact of carbon elements with solder paste, the lead plating layer is directly contacted with the solder paste, that is, when the solder paste is filled into the carbon grid, the solder paste is adhered to the thin lead plating layer, so that the affinity between the solder paste and the carbon grid can be improved, that is, the affinity between the solder paste and the solder paste can be improved, but because lead metal is a heavy metal, the lead metal has certain toxicity, the use of lead metal needs to be reduced while the affinity between the solder paste is ensured, and therefore, the thickness of the copper layer of the substrate is 2 micrometers to 5 micrometers; the thickness of the thin lead plating layer is 6-15 microns, on one hand, enough adhesiveness and tin paste affinity can be ensured, the use of lead metal can be reduced as much as possible, and the thickness of 6-15 microns is also really thin, namely the plating layer is the thin lead plating layer.
In order to enable the carbon grid to better support the locked and cured tin paste of the lead-carbon battery, and the problem that the tin paste is not easy to soften, loosen and collapse is preferably solved, after the step S190, the carbon grid is immersed into a mixed solution of graphene and water, and after the carbon grid with graphene particles adhered to the surface is fished out, hot air drying operation is performed; drying the carbon plate grid with the graphene particles adhered to the surface at 75-80 ℃; preparing lead-carbon battery tin paste; the lead-carbon battery tin paste comprises the following components in parts by mass: 100-120 parts of lead powder; 1-1.6 parts of flaky high-purity graphite powder; 0.5-1.2 parts of high-purity carbon nano tubes; 80-90 parts of polytetrafluoroethylene emulsion; 0.5 to 0.8 portion of acetylene black(ii) a 4-15 parts of red lead; 1-6 parts of activated carbon; 20-37 parts of basalt fibers; 60-75 parts of polypropylene fiber; 20-28 parts of carbon nanofibers; 8-16 parts of sulfuric acid; 6-8 parts of pure water; and filling the lead-carbon battery tin paste into the carbon grid, and drying and curing to obtain the lead-carbon battery anode. Preferably, the preparation method of the mixed solution of graphene and water comprises the following steps: preheating water to 75-80 ℃; adding a dispersing agent into water in advance, stirring and mixing, and then adding graphene particles to obtain a mixed solution of graphene and water; keeping the temperature of the mixed liquid of the graphene and the water at 75-80 ℃, and immersing the carbon grid into the mixed liquid of the graphene and the water, so that the dispersity of the graphene can be improved, and the adhesion of the graphene and the carbon grid can be improved; the mixed liquid immersion and medium and low temperature drying operations are sequentially carried out, so that graphene particles can be sparsely and uniformly distributed on the thin lead coating, the graphene particles are matched with the electric conductor of the lead-carbon battery tin paste, such as flaky high-purity graphite powder, high-purity carbon nano tubes, nano carbon fibers and the like, the internal resistance of contact between an active material and a grid can be reduced, the electrical property is better, meanwhile, the locked and cured lead-carbon battery tin paste can be better supported due to the fact that the graphene particles protrude out of the thin lead coating, compared with the traditional lead-carbon battery tin paste, the lead-carbon battery tin paste has the advantages that the conductivity is greatly improved by adding the flaky high-purity graphite powder, the high-purity carbon nano tubes and acetylene black, the large-current discharge performance can be improved, the content of sulfuric acid is not high, and the lead-carbon battery tin paste is easier to be formed, and further the utilization rate of the active substance can be improved. Because the heavy-current discharge performance is better, the red lead and the activated carbon are introduced, the porosity and the fluffy degree of the lead-carbon battery tin paste can be fully ensured, the adsorption to the electrolyte is stronger, and the continuity and the safety of the reaction are also considered. The flaky high-purity graphite powder has a better surface effect, can be in more sufficient contact with lead powder, has a larger surface area, and the high-purity carbon nano tube also has the effect, so that the high-current discharge performance is further improved. The acetylene black has both electrolyte adsorption performance and large-current discharge performance. Secondly, by polymerizationThe tetrafluoroethylene emulsion serving as an efficient binder can be firmly combined with scale-shaped high-purity graphite powder, high-purity carbon nano tubes, acetylene black, basalt fibers, polypropylene fibers and carbon nano fibers, the problem of mechanical structure integrity reduction caused by adding electric conductors, particularly acetylene black and active carbon, can be greatly improved, meanwhile, polytetrafluoroethylene, the basalt fibers, the polypropylene fibers and the carbon nano fibers can be mutually matched, and multiple parts of polytetrafluoroethylene, the basalt fibers, the polypropylene fibers and the carbon nano fibers form a uniform net structure, so that the toughness and the shock resistance of the lead-carbon battery tin paste are improved. Furthermore, the carbon nanofibers can serve as a conductor to reinforce the charge and discharge performance and can also play a role in structure reinforcement, thereby achieving two purposes. Finally, because the basalt fiber, the polypropylene fiber, the carbon nanofiber and the binder form a net structure, and the lead powder, the flaky high-purity graphite powder, the high-purity carbon nanotube, the acetylene black, the red lead and the activated carbon are granular or flaky structures, the lead powder, the flaky high-purity graphite powder, the high-purity carbon nanotube, the acetylene black, the red lead and the activated carbon can be well filled into net-shaped gaps, so that the conductivity can be improved, and the conductive carbon also has good mechanical properties. Preferably, the oxidation degree of the lead powder is 65% -75%; the apparent density of the lead powder is 1.6g/cm3～1.8g/cm3. Preferably, the sulfuric acid has a density of 1.2g/cm at 25 degrees Celsius3. Preferably, the polypropylene fibers comprise polypropylene long fibers and/or polypropylene short fibers; the length of the polypropylene long fiber is 2-4 mm, and the diameter of the polypropylene long fiber is 5-15 nm; the length of the polypropylene short fiber is 6-10 mm, and the diameter of the polypropylene short fiber is 5-15 nm. The basalt fibers comprise basalt long fibers and/or basalt short fibers; the length of the basalt long fiber is 4 mm-6 mm, and the diameter of the basalt long fiber is 6 nm-20 nm; the length of the basalt short fiber is 8-15 mm, and the diameter of the basalt short fiber is 6-20 nm. Further, the polypropylene fiber comprises polypropylene long fiber and polypropylene short fiber; the length of the polypropylene long fiber is 2-4 mm, and the diameter of the polypropylene long fiber is 5-15 nm; the length of the polypropylene short fiber is 6-10 mm, and the diameter of the polypropylene short fiber is 5-15 nm; the basalt fiber comprises basalt long fiber and basalt short fiberFibers; the length of the basalt long fiber is 4 mm-6 mm, and the diameter of the basalt long fiber is 6 nm-20 nm; the length of the basalt short fiber is 8-15 mm, the diameter of the basalt short fiber is 6-20 nm, and therefore, the basalt short fiber and the polypropylene short fiber are used in a composite mode, the long fiber and the short fiber form a main framework of a net structure through the long fiber and polytetrafluoroethylene, the short fiber can be filled to well solve the problem that the space of a net-shaped inner cavity is large due to the long fiber, and the lead-carbon battery tin paste granular or sheet structure raw material can be better prepared. Further, in the basalt fiber and the polypropylene fiber, the mass ratio of the long fibers to the short fibers is 3: 1.
the above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (7)

1. The electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery is characterized by comprising the following steps of:
s110: mixing and stirring a carbon raw material and a binder to obtain mixed carbon slurry;
s120: filling the mixed carbon slurry into a forming die, and performing extrusion forming to obtain a carbon grid;
s130: sequentially carrying out oil removal operation and water washing operation on the carbon grid;
s140: carrying out high-temperature baking operation on the carbon plate grid;
s150: carrying out coarsening operation and washing operation on the carbon grid in sequence;
s160: by SnCl2Sensitizing the carbon grid by using the solution, and then washing;
s170: using PdCl2The solution is used for activating the carbon grid,then, carrying out water washing operation;
s180: placing the carbon plate grid in copper plating solution, carrying out copper plating operation to form a substrate copper layer on the surface of the carbon plate grid, and then carrying out water washing operation;
s190: placing the carbon plate grid in a lead plating solution, performing lead plating operation to form a thin lead plating layer on the surface of the substrate copper layer, and then performing water washing operation;
wherein the carbon raw material is at least one of flight graphite, all-carbon aerogel, foam carbon, conductive graphite, carbon black and acetylene black; before mixing and stirring the carbon raw material and the binder, mixing and stirring the carbon raw material by adopting ethanol water solution in advance; and before the oil removing operation is carried out on the carbon grid, carrying out extrusion shaping operation on the carbon grid.
2. The electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery according to claim 1, wherein after the lead coating operation and the water washing operation are sequentially performed, a vacuum drying operation is further performed on the carbon grid by using vacuum drying equipment.
3. The electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery as claimed in claim 1, wherein the high-temperature baking operation is performed by using an oven at a temperature of 550-600 ℃, and the high-temperature gas in the oven is continuously pumped out while the dry inert gas is supplemented into the oven.
4. The electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery as claimed in claim 1, wherein the roughening operation is performed by immersing the carbon grid into a roughening solution at a temperature of 85-100 ℃.
5. The method of electroplating thin lead plating on a carbon grid of a lead-carbon battery as claimed in claim 1, wherein the copper plating solution comprises a copper salt, a complexing agent, a reducing agent, an accelerator and an inhibitor.
6. The electroplating method of the thin lead coating of the carbon grid of the lead-carbon battery according to claim 1, wherein the thickness of the substrate copper layer is 2-5 microns;
the thickness of the thin lead plating layer is 6-15 microns.
7. The method of electroplating the lead-carbon battery carbon grid thin lead coating according to claim 1, wherein the carbon grid is filled with solder paste for adhering the solder paste to the thin lead coating.
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Denomination of invention: Electroplating Method of Thin Lead Plating on Carbon Grid of Lead Carbon Batteries

Effective date of registration: 20230317

Granted publication date: 20210420

Pledgee: Bank of Beijing Limited by Share Ltd. Shenzhen branch

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