CN111682218A - Enhanced carbon-containing material current collector and preparation method thereof - Google Patents
Enhanced carbon-containing material current collector and preparation method thereof Download PDFInfo
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
- H01M4/14—Electrodes for lead-acid accumulators
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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
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- H—ELECTRICITY
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- 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
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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
- H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an enhanced carbon-containing material current collector, wherein the material of the current collector comprises a carbon-containing material, the carbon-containing material is used as a base material, a conductive metal coating is directly electroplated on the base material, and the carbon-containing material base material is subjected to dipping and graphitization treatment. The invention relates to an enhanced carbon-containing material current collector and a preparation method thereof, wherein the current collector adopts a carbon-containing material as a base material, the porosity of the base material is reduced by an impregnation method for the base material, the density is improved, the compressive strength is increased, the resistivity is reduced, the physical and chemical properties are changed, then a coating is directly electroplated on the surface of the base material, a transition layer is not needed to be plated due to the treatment of the impregnation method, a target conductive material is electroplated, and the current collector can be used as an anode current collector or a cathode current collector.
Description
Technical Field
The invention relates to the technical field of storage batteries, in particular to a current collector of an enhanced carbon-containing material and a preparation method thereof.
Background
Since birth, lead-acid storage batteries have been widely developed due to their high cost performance, high safety and reliability and recyclable characteristics, and have been well applied in the fields of electric vehicles and communications. However, the traditional lead-acid storage battery adopts heavy metal lead, so that the weight and the volume of the battery are large, and the application of the lead-acid storage battery in many fields is seriously influenced.
To solve this problem, many technicians have made great efforts for this purpose, and various methods have been adopted to solve the problem. Many technicians consider using other corrosion resistant alloys to replace the positive and negative lead alloys in the positive and negative grids (current collectors) of the battery. Technicians replace lead alloy with metal titanium, but the price of titanium metal is high, and the combination of the surface of the titanium metal or the alloy and lead is not firm, so that the service life cannot be ensured, and basically no one really applies the lead alloy to products. In large batteries, copper plate grid is plated with lead and lead-tin alloy as negative plate grids (current collectors), but copper has high density and high price, and is used only in applications without considering cost (submarine batteries) and cannot be used in positive electrodes.
Technical personnel adopt light metal aluminum as a matrix to electroplate lead or tin and other corrosion-resistant materials to manufacture the grid, but because the electroplated layer always has defects, aluminum can be dissolved out under acidic conditions and alkaline conditions, adverse effects are brought to current collectors and active substance structures, and production is not realized.
Technical personnel also adopt the plastic surface to electroplate lead alloy to replace lead alloy, because common plastic is not conductive, the difficulty of plastic lead alloy electroplating is also larger, a transition layer needs to be modified on the plastic surface, and transition layer metal outwards adopts solutions such as nickel, copper and the like to form a covering material on the plastic surface, but outwards can not be suitable for systems with corrosive electrolyte, such as lead-acid storage batteries and the like. In addition, the plating layer needs to have a certain thickness to achieve good conduction. Therefore, there have been attempts by the skilled person to use conductive plastics, but the conductive plastics have limited conductive ability and are expensive, resulting in the failure of this technical route.
In the prior art, titanium dioxide or graphite and other materials are mixed with plastics to prepare a current collector framework, and then surface electroplating is carried out to form a conductive layer, but because the plastics basically have no conductive function, the mixed conductive materials cannot form a conductive network, only have weak conductive function, electroplating is difficult to carry out, and even a transition layer is chemically plated to form conductivity first, and then electroplating of a target material is carried out. Actually, the surface modification of the plastic surface is equivalent to the surface modification of conductivity, the transition layer is generally subjected to surface treatment by nickel, chromium, copper and the like, and obviously, a plating layer containing the elements is unfavorable for the battery.
The invention with publication number CN107069106A discloses that the positive plate and the negative plate are made of mesh woven by high-strength conductive fiber as bottom plates, the positive plate and the negative plate are respectively coated with positive active material and negative active material, the high-strength conductive fiber is one or more of glass fiber, carbon fiber and metal wire, the patent discloses a woven grid, but the woven grid requires high conductivity in the selection process of fiber, the pole plate material uses mesh woven by high-strength fiber material with good conductivity as the base material of the pole plate, the battery active material is uniformly coated on the base material, because the mesh woven by high-strength fiber material has much larger surface area as the base material of the pole plate compared with lead plate with the same area, the conductivity and adhesive force between the base material and the battery active material coated thereon are improved, the strength of the polar plate is greatly improved compared with the original lead foil, and the polar plate is easier to process compared with the original lead foil, but the selected braided material is difficult to ensure the conductivity, and although the active substance can have good fixation fastness with the braided fabric, the generation of heat caused by overlarge resistance cannot be avoided in the using process, and the use stability of the battery under the high-temperature condition is reduced.
Therefore, the design of a novel current collector is important, so that the mass of positive and negative grids of the storage battery can be reduced, the framework strength of the current collector can be enhanced, a target plating layer can be conveniently electroplated, and the chemical performance can be enhanced.
Disclosure of Invention
Aiming at the problems in the prior art, the current collector adopts the carbon-containing material as the base material, the porosity of the base material is reduced by an impregnation method for the base material, the density is improved, the compressive strength is increased, the resistivity is reduced, the physical and chemical properties are changed, then a plating layer is directly electroplated on the surface of the base material, a transition layer is not needed to be plated due to the treatment of the impregnation method, the current collector can be used as a positive electrode current collector or a negative electrode current collector after a target conductive material is electroplated, and the current collector prepared by adopting the carbon-containing material and the method has strong chemical properties and long service life.
The specific technical scheme is as follows:
the current collector comprises a substrate and a coating.
The structure and the material of the current collector are improved, the structure of the base material electroplating coating is designed, a transition layer is not needed, the problems that the transition layer is not corrosion-resistant and electrolyte is damaged are solved, the light carbon-containing material can be selected as the base material based on the fact that the existing current collector is made of the lead alloy material in consideration of the requirement of light weight of the lead-acid storage battery, and the effect of reducing the quality of the current collector is achieved integrally.
Further, in order to ensure creep resistance and mechanical properties of the current collector, the thickness of the substrate/plating layer of the present invention is 2 to 50, and further preferably 2 to 25. The thickness of the coating is 0.02-2mm, and the thickness of the base material is 0.2-4 mm.
The current collector is used as a key structure of the lead-acid storage battery, the cycle times and the service life of the lead-acid storage battery can be influenced by the creep resistance, the mechanical property and the like of the current collector, and if the creep resistance of the current collector is poor, the current collector easily causes the falling of active substances in the recycling process, so that the service life is shortened. The invention uses the structure of the base material electroplating coating, the thickness of the coating and the thickness of the base material in the structure have great influence on the creep property of the current collector, for example, when the size of the coating is too small, after the active substances are attached, the current collector is easy to deform under the action of the external force brought by the acid environment and the active substances, therefore, the invention adjusts the structure size of the base material electroplating coating according to the requirements of cycle times and service life, and finds that the service life and the cycle times can reach the requirements in the prior art under the conditions that the thickness of the base material/coating is 2-50, preferably 2-25, the thickness of the coating is 0.02-2mm, and the thickness of the base material is 0.2-4mm, and the quality of the prepared grid can be obviously reduced and even reduced by more than 5-50%.
The base material is a carbon-containing material, and the plating layer is a conductive material.
Furthermore, as a current collector material, the current collector material is required to have good conductivity and corrosion resistance, in order to avoid possible electrochemical reactions of different materials in the structural material of the electroplating coating of the base material, the carbon-containing material is added into the base material, and the corrosion resistance of the carbon-containing material is mainly utilized to further avoid the generation of electrochemical corrosion of the carbon-containing material.
Further the carbonaceous material comprises one or more of graphite, carbon black, activated carbon or carbon fibers.
Further, the enhanced carbon-containing material is subjected to impregnation and graphitization treatment.
The graphite has excellent conductivity, can improve the mechanical property of the composite material, and can greatly improve the corrosion resistance of the current collector by using the graphite as a base material of the current collector. However, when the metal layer is electroplated, the electroplating process is easy to encounter certain difficulties due to the strength difference of the graphite material, and the service life of the final storage battery is also influenced; in order to solve the problems, the invention provides an impregnation method, namely a process for reducing the porosity of a product, improving the density and increasing the compressive strength, in addition, the resistivity of a finished product can be reduced and the physical and chemical properties of the product can be changed by graphitizing a carbon material, and the carbon materials are mutually connected, so that the current collector (grid) has stronger conductive capability. The good conductivity is beneficial to directly electroplating target metal or metal alloy without a transition layer, so that the conductive material can be used as a positive electrode or negative electrode current collector. The problem that the strength of the electroplated grid can not meet the requirement due to low strength of common carbon materials is solved.
The substrate resistivity of the current collector of the enhanced carbon-containing material is 0.1 × 10-7Ω·m-2.0×10-7Ω · m, more preferably 0.5 × 10-7Ω·m-1.5×10-7Ω · m, more preferably 1.0 × 10-7Ω·m-1.5×10-7Ω·m。
The tensile strength of the base material carbon-containing material is more than 55N/mm2Further preferred is a tensile strength of greater than 60N/mm2。
The conductivity of the current collector is an essential requirement for whether the current collector can be used as a grid, and the mechanical property of the current collector is required, because the current collector is of a substrate electroplating coating structure, the substrate is a substrate material of the current collector, the substrate is required to have excellent mechanical property, the current collector further selects a plurality of blending preparation materials of graphite, carbon black, activated carbon or carbon fiber through the adjustment of the substrate material, including but not limited to the adjustment of the graphite dosage, and ensures that the resistivity of the current collector is 0.1 × 10-7Ω·m-2.0×10-7Ω · m, more preferably 0.5 × 10-7Ω·m-1.5×10-7Ω · m, more preferably 1.0 × 10-7Ω·m-1.5×10-7Omega.m, and simultaneously satisfies that the tensile strength of the carbon-containing material of the base material is more than 55N/mm2Further preferred is a tensile strength of greater than 60N/mm2。
Further, the plating layer is made of a metal conductive material.
Further preferably, the metal in the metal conductive material is one or more of copper, aluminum, lead, zinc, tin and titanium.
For the light weight of the slab lattice, the prior art mostly uses the foam slab lattice or adds light metal to replace lead metal, so as to achieve the effect of light weight, and for the foam slab lattice, the adhesive force of the foam slab lattice to active substances can be improved to a certain extent, but certain defects exist for the mechanical property, and for adding the light metal in the alloy, the light weight degree is smaller.
According to the invention, through the electroplating coating structure of the base material, a light base material can be selected, and the base material can be selected in a larger proportion on the premise of ensuring the conductivity, mechanical property and corrosion resistance of the base material, so that the quality of the grid is greatly reduced on the premise of ensuring the performance of the current collector. For the plating layer, good electrical conductivity must be ensured.
The material selection of the current collector needs to have excellent conductivity, only the conductivity is good, the heat energy generated by the conductivity can be avoided in the use process of the lead-acid storage battery, the expansion of the electrolyte and the whole battery is further prevented, the falling of active substances is prevented, and the technical effect of prolonging the service life is achieved-7Ω·m-4×10-7Ω · m, more preferably 1.0 × 10-7Ω·m-3.0×10-7Ω · m, more preferably 1.5 × 10-7Ω·m-2.5×10-7Omega.m. In addition to the mechanical property and the chemical property, the light weight selection is also considered, and the effect of reducing the mass of the current collector is achieved.
The invention also provides a preparation method of the enhanced carbon-containing material current collector, which comprises the step of obtaining the carbon-containing material current collector by directly electroplating a coating after the base material is formed through dipping and graphitization treatment.
Specifically, the method comprises the following steps: (1) forming a base material;
and (3) pressing the carbon material into a grid shape through a die.
(2) Dipping the base material;
and (2) soaking the carbon material grid base material in the step (1) into solutions such as phenolic resin, epoxy resin and polyurethane, so that the solution can be filled into gaps of the carbon material, the porosity of the base material is reduced, the mechanical property of the base material is further enhanced, and the guarantee of the mechanical property is provided for subsequent electroplating.
(3) Carrying out graphitization treatment on the base material;
under the condition of high temperature, the grid base material is sintered, so that the grid material is graphitized, and the graphitized grid base material has good conductivity, and the performance can reduce the thermal expansion of the battery in the use process, prevent the falling of active substances and further prolong the service life of the storage battery.
(4) And electroplating the coating to obtain the carbon-containing material current collector.
(5) And (4) carrying out subsequent operation on the current collector in the step (4) to obtain an electrode, and preparing the lead-acid storage battery.
Specifically, the current collector obtained in the step (4) is subjected to paste coating, curing, lamination, cast welding, groove entering, cover sealing, terminal welding, terminal sealing, formation, safety valve installation and warehousing.
The invention can prepare base materials with different thicknesses by controlling the conditions of electrolyte concentration, electrolysis time, electrolysis voltage and the like, and electroplate different coatings by controlling the electroplating conditions so as to prepare current collectors with different specifications.
Compared with the arrangement of the transition layer in the prior art, the transition layer does not need to be coated, the problems that the transition layer is not corrosion-resistant and electrolyte is damaged are solved, meanwhile, the arrangement of the transition layer is not needed, the technological process can be reduced, and the material for preparing the current collector can be obtained by directly electroplating the coating. By adopting the preparation method, the process material is saved, the process steps are reduced, the key is that the mechanical property and the chemical property of the prepared current collector material are enhanced, the service life of the current collector is prolonged, and the preparation and use requirements of the current collector are met.
Compared with the prior art, the enhanced carbon-containing material current collector prepared by the invention has the advantages of strong conductivity, strong tensile strength, excellent corrosion resistance, excellent electrochemical reversibility, strong electrochemical activity and the like, the quality of the current collector is greatly reduced compared with the prior art, the lightweight requirement is met, and meanwhile, the preparation method is simple and the operation is controllable.
Drawings
Fig. 1 is a flow chart of a process for preparing a current collector of the enhanced carbonaceous material of the present invention;
FIG. 2 is a diagram illustrating a carbon material molding step in the present invention;
FIG. 3 is a diagram of a plating step in the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a current collector of an enhanced carbon-containing material, which comprises the steps of forming a base material, and then directly electroplating a coating after dipping and graphitization treatment to obtain the current collector of the carbon-containing material.
Specifically, the method comprises the following steps: (1) forming a base material;
and (3) pressing the carbon material into a grid shape through a die.
(2) Dipping the base material;
and (2) soaking the carbon material grid base material in the step (1) into solutions such as phenolic resin, epoxy resin and polyurethane, so that the solution can be filled into gaps of the carbon material, the porosity of the base material is reduced, the mechanical property of the base material is further enhanced, and the guarantee of the mechanical property is provided for subsequent electroplating.
(3) Carrying out graphitization treatment on the base material;
under the condition of high temperature, the grid base material is sintered, so that the grid material is graphitized, and the graphitized grid base material has good conductivity, and the performance can reduce the thermal expansion of the battery in the use process, prevent the falling of active substances and further prolong the service life of the storage battery.
(4) And electroplating the coating to obtain the carbon-containing material current collector.
(5) And (4) carrying out subsequent operation on the current collector in the step (4) to obtain an electrode, and preparing the lead-acid storage battery.
The first embodiment is as follows:
the invention relates to preparation of an enhanced carbon-containing material current collector, which specifically comprises the steps of taking a graphite material as a substrate additive, pressing and molding the substrate, and then directly electroplating a coating after dipping and graphitization treatment to obtain the substrate of the carbon-containing material current collector.
It can be seen from the above embodiments that the higher the content of the graphite serving as the carbon-containing material of the base material is, the better the tensile strength and the conductivity of the current collector are, and the alloy material is selected as the plating material, so that the performance of the current collector can be further improved.
Example two:
the invention relates to preparation of a reinforced carbon-containing material current collector, which comprises the steps of changing the thicknesses of a base material and a coating, pressing and molding the base material, and directly electroplating the coating after dipping and graphitization treatment to obtain the carbon-containing material current collector.
From the above experiment, it can be seen that, on the basis of the first embodiment, the tensile strength and the conductivity of the current collector can be changed by changing the thicknesses of the base material and the plating layer, and the performance is optimal when the thickness of the base material/the plating layer is 2-25.
In conclusion, the enhanced carbon-containing material current collector prepared by the invention has the advantages of strong conductivity, strong tensile strength, excellent corrosion resistance, excellent electrochemical reversibility, strong electrochemical activity and the like, and compared with the prior art, the quality of the current collector is greatly reduced, the light weight requirement is met, and meanwhile, the preparation method is simple and the operation is controllable.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. The material of the current collector comprises a carbon-containing material, the carbon-containing material is used as a base material, a conductive metal coating is directly electroplated on the base material, and the carbon-containing material base material is subjected to dipping and graphitization treatment.
2. The enhanced carbon-containing material current collector of claim 1, wherein: the substrate thickness/plating thickness is 2 to 50, further preferably 2 to 25; the thickness of the coating is 0.02-2mm, and the thickness of the base material is 0.2-4 mm.
3. The enhanced carbon-containing material current collector of claim 1, wherein: the carbon material includes one or more of graphite, carbon black, activated carbon, or carbon fiber.
4. The enhanced carbon-containing material current collector of claim 1, wherein the substrate resistivity of the current collector is 0.1 × 10-7Ω·m-2.0×10-7Ω · m, more preferably 0.5 × 10-7Ω·m-1.5×10-7Ω · m, more preferably 1.0 × 10-7Ω·m-1.5×10-7Omega.m; the tensile strength of the base material carbon-containing material is more than 55N/mm2Further preferred is a tensile strength of greater than 60N/mm2。
5. The enhanced carbon-containing material current collector of claim 1, wherein: the metal in the conductive metal plating layer is one or more of copper, aluminum, lead, zinc, tin and titanium.
6. The reinforced carbonaceous material current collector of claim 1, wherein the current collector has an electrical resistivity of 0.02 × 10-7Ω·m-4×10-7Ω · m, more preferably 1.0 × 10-7Ω·m-3.0×10-7Ω · m, more preferably 1.5 × 10-7Ω·m-2.5×10-7Ω·m。
7. An electrode prepared using a current collector of an enhanced carbonaceous material as claimed in any one of claims 1 to 6.
8. A lead-acid battery prepared using the electrode of claim 7.
9. The method for preparing the enhanced carbon-containing material current collector as claimed in any one of claims 1 to 6, wherein the method comprises the step of directly electroplating the plated layer after the substrate is formed by dipping and graphitization treatment.
10. The method for preparing the enhanced carbon-containing material current collector of any one of claim 9, comprising the steps of:
(1) forming a base material, namely pressing a carbon material into a grid shape through a die;
(2) dipping the base material;
dipping the carbon material grid base material in the step (1) into the solution, so that the solution can be filled in the gaps of the carbon material, the porosity of the base material is reduced, the mechanical property of the base material is further enhanced, and the guarantee of the mechanical property is provided for subsequent electroplating;
(3) carrying out graphitization treatment on the base material;
under the condition of high temperature, the grid base material is sintered, so that the grid material is graphitized, and the graphitized grid base material has good conductivity, and the performance can reduce the thermal expansion of the battery in the use process, prevent the falling of active substances and further prolong the service life of the storage battery;
(4) and cleaning and drying the electroplated layer to obtain the enhanced carbon-containing material current collector.
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