CN114975895A - Positive electrode lead paste and positive electrode of lead-acid battery, preparation method of positive electrode, battery and electric vehicle - Google Patents
Positive electrode lead paste and positive electrode of lead-acid battery, preparation method of positive electrode, battery and electric vehicle Download PDFInfo
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- CN114975895A CN114975895A CN202210645497.7A CN202210645497A CN114975895A CN 114975895 A CN114975895 A CN 114975895A CN 202210645497 A CN202210645497 A CN 202210645497A CN 114975895 A CN114975895 A CN 114975895A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
- B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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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
- H01M10/12—Construction or manufacture
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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
- H01M4/16—Processes of manufacture
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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
Abstract
The invention discloses a positive pole lead paste of a lead-acid battery, a positive pole, a preparation method of the positive pole lead paste, the battery and an electric vehicle, wherein the positive pole lead paste contains MXene materials and/or MXene-MAX heterojunction materials, the invention also comprises a lead-acid battery positive pole prepared from the positive pole lead paste and a lead-acid battery containing the lead-acid battery positive pole.
Description
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to a positive lead paste and a positive electrode of a lead-acid battery, a preparation method of the positive lead paste and the positive electrode, the battery and an electric vehicle.
Background
In the current battery market, because the lead-acid battery has the advantages of high cost performance, high recovery rate, wide application temperature range, safety, reliability and the like compared with a lithium battery, the lead-acid battery is still a secondary battery with a large share and a wide application range in the battery market, and is particularly applied to the fields of large-scale energy storage and the like. The lead-acid battery is the storage battery with the largest output in China, and the output of the lead-acid battery in China ranks the first in the world.
The lead-acid storage battery negative active material sponge lead has good conductivity and high porosity; in contrast, the positive electrode active material PbO 2 The conductivity is obviously poor, and the porosity is low. After normalization, the positive plate PbO 2 The content is still low, the resistance of the anode active material is high, and the low-temperature performance and the power characteristic of the battery are obviously influenced. And the covering effect of the discharge product lead sulfate and the electric conduction capability of lead dioxide are poor, and the ohmic polarization is very serious at the end of discharge, so that the voltage is rapidly reduced, the utilization rate of active substances is low, and the battery capacity is rapidly reduced. In order to improve the electrochemical performance of the positive electrode of a lead-acid battery, a large amount of conductive agent, such as carbon-containing components such as graphite, graphene, carbon fiber and the like, is usually added during paste mixing, and the addition of the conductive agent can improve the initial performance of the battery, but the positive electrode of the lead-acid battery has strong oxidizing property, so that the carbon-containing conductive agent is oxidized into carbon dioxide at the initial stage of circulation, the structural strength of an active material is reduced, and the service life of the battery is shortened. Also, some ceramic conductive additives such as SnO 2 、Ti 4 O 7 、BaPbO 3 The like, but lead dioxide and lead sulfate have large volume change in the charge-discharge cycle of the lead-acid battery due to uncontrollable morphology and smooth particles thereof (>90%), leading to the positive active material being easy to soften and fall off, causing the strength of the positive plate of the battery to be reduced, leading to the lead-acid battery to lose efficacy in advance of the mud falling of the lead plaster.
Disclosure of Invention
Aiming at the problems of the positive electrode of the lead-acid battery, the invention provides a novel conductive two-dimensional material MXene material and/or MXene-MAX heterojunction material as a conductive agent, and lead-acid battery positive lead paste and the lead-acid battery thereof, so as to improve the generation rate of lead dioxide in the formation process, reduce the ohmic resistance of the electrode and improve the cycle stability and the rate capability of the lead-acid battery.
The invention provides positive electrode lead paste of a lead-acid battery, which contains MXene material and/or MXene-MAX heterojunction material.
In some embodiments, the MXene material has a chemical formula of M n+1 X n T x Wherein M is selected from one or more transition metal elements, X is selected from one or more carbon, nitrogen or boron elements, T x Represents a functional group including-F, -Cl, Br, I, -O, -S, -OH, -NH 4 N is more than or equal to 1 and less than or equal to 4; preferably, M is selected from at least one of Ti, V, Mo, Nb, Ta, W, Cr.
In some embodiments, the chemical formula of the MXene-MAX heterojunction material is represented by M n+1 X n -M n+1 AX n Wherein M is selected from one or more transition metal elements, A is selected from elements of a third main group and/or a fourth main group, X is selected from one or more carbon, nitrogen or boron elements, and n is more than or equal to 1 and less than or equal to 4; preferably, the M is selected from at least one of Ti, V, Mo, Nb, Ta, W and Cr; the A is selected from Al, Sn or Si elements.
In some embodiments, the mass percentage of the MXene material and/or the MXene-MAX heterojunction material in the dry material of the positive electrode lead paste is between 0.1% and 80%.
In some embodiments, MAX phase material is also included in the positive electrode lead paste.
In some embodiments, the positive electrode lead paste comprises, in parts by weight: 50-90 parts of lead powder and/or lead-containing compound powder; 0.01 to 50 parts of MXene material and/or MXene-MAX heterojunction material.
In some embodiments, the lead-containing compound powder includes: one or more of basic lead sulfate, lead oxide and red lead.
The second aspect of the present invention provides a method for preparing positive electrode lead paste, comprising the steps of: mixing lead powder or lead-containing compound powder, MXene material and/or MXene-MAX heterojunction material to obtain dry material mixture; adding water and a sulfuric acid solution into the dry material mixture, and stirring and mixing to obtain a wet material mixture; and standing and curing the wet material mixture to obtain the composite positive lead plaster.
The invention provides the application of the MXene material and/or the MXene-MAX heterojunction material as the positive electrode additive of the lead-acid battery.
The invention provides a lead-acid battery anode, which contains MXene material and/or MXene-MAX heterojunction material.
The fifth aspect of the invention provides a preparation method of the lead-acid battery positive electrode, which is characterized in that the positive electrode lead plaster is prepared; or coating the positive lead plaster obtained by the preparation method on a grid to prepare the lead-acid battery positive electrode.
The sixth aspect of the invention provides a lead-acid battery, which contains the positive electrode of the lead-acid battery; or the lead-acid battery positive electrode obtained by the preparation method.
The seventh aspect of the invention provides an electric vehicle containing the lead-acid battery.
An eighth aspect of the invention provides a vehicle containing the lead-acid battery.
The invention provides an application of MXene material and/or MXene-MAX heterojunction material as additive for a lead-acid battery anode, and the excellent technical effects are as follows:
1. the MXene material and/or MXene-MAX heterojunction material has excellent conductivity, and the conductivity of the positive electrode material can be effectively improved when the MXene material and/or MXene-MAX heterojunction material are added into the positive electrode of the lead-acid battery, so that the conversion efficiency of lead dioxide in the formation process can be improved, the conductivity of the whole electrode can be improved, and the rate capability and the cycle stability of lead acid are improved;
2. the MXene material and/or MXene-MAX heterojunction material disclosed by the invention has excellent corrosion resistance and oxidation resistance, is not easy to oxidize and corrode in a lead-acid battery anode material and in a sulfuric acid electrolyte environment, can improve the conductivity of the lead-acid battery and ensure the stability of the lead-acid battery anode, and avoids the permanent loss of the energy density and the cycle life of the battery caused by the oxidation and corrosion of the lead-acid battery anode.
3. The MXene material and/or MXene-MAX heterojunction material has a high specific surface area, the contact area of the MXene material and the positive electrode lead paste is increased, particularly the MXene-MAX heterojunction material has an open accordion shape, the positive electrode lead paste can be dispersed in the positive electrode lead paste, the problem that the positive electrode of the lead-acid battery is easy to soften and fall off is solved, and the service life and the rate capability of the lead-acid battery are prolonged.
Drawings
FIG. 1 is a schematic diagram showing the relationship between the preparation processes of a MAX phase material, an MXene-MAX heterojunction material and an MXene material in the present invention;
FIG. 2 shows the MAX phase material Ti 3 AlC 2 The high-resolution electron microscope picture and the structural schematic diagram (a) and the lattice spacing analysis picture (b) thereof; a high-resolution electron microscope photograph of the MXene-MAX heterojunction material, a structural schematic diagram (c) and a lattice spacing analysis photograph (d) thereof;
FIG. 3 shows accordion-like MXene material Ti in example 2 of the present invention 3 C 2 F x XRD spectrum (a) and SEM photograph (b) of (a);
FIG. 4 shows a two-dimensional MXene material Ti in embodiment 3 of the present invention 3 C 2 F x XRD spectrum (a) and SEM photograph (b) of (a);
FIG. 5 shows a MAX phase material Ti in example 5 of the present invention 3 AlC 2 (a) And MXene-Ti 3 AlC 2 SEM photograph (b) of the heterojunction material.
Detailed Description
The technical solution of the present invention will be described below by way of specific examples. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The MXene materials, MXene-MAX heterojunction materials, and MAX phase materials used in the examples were purchased from Beijing Santana Engineers, Inc., other materials and instruments, and their sources are not particularly limited, and may be purchased commercially or prepared by conventional methods known to those skilled in the art.
The MXene phase material is obtained by etching the component A in a MAX phase material, and the MXene-MAX heterojunction material with the surface having the characteristics of an accordion MXene material and the interior having the characteristics of the MAX phase material and similar to a sea urchin structure is obtained by controlling the etching degree. The material preparation process is schematically shown in figure 1. We use Ti 3 AlC 2 For the purpose of illustration, the characteristics of this MXene-MAX heterojunction material are shown in FIG. 2, where FIG. 2a and FIG. b show the MAX phase material Ti 3 AlC 2 The high-resolution electron microscope photograph and the structural schematic diagram (a) and the lattice spacing analysis photograph (b) thereof; FIGS. 2c and d show Ti 3 AlC 2 Partially etched MXene-MAX heterojunction material (denoted as MXene-Ti) 3 AlC 2 ) The high-resolution electron microscope picture (c) and the lattice spacing analysis picture (d) can show MXene-Ti by contrast 3 AlC 2 Is obviously different from Ti 3 AlC 2 The surface exhibits characteristics of MXene.
Example 1
The embodiment provides a positive lead plaster and a preparation method thereof, wherein the positive lead plaster comprises the following components in parts by weight: 50-90 parts of lead powder, 0.01-50 parts of MXene material and/or MXene-MAX heterojunction material, 0.1-20 parts of tetrabasic lead sulfate, 3-15 parts of sulfuric acid solution, 0-2 parts of fiber material and 5-20 parts of water.
In a preferred embodiment, the positive electrode lead paste comprises, in parts by weight: 70-90 parts of lead powder, 0.01-20 parts of MXene material and/or MAX phase material, 0.1-20 parts of tetrabasic lead sulfate, 3-15 parts of sulfuric acid solution, 0-2 parts of fiber material and 5-20 parts of water.
In another preferred embodiment, the positive electrode lead paste includes, in parts by weight: 70-90 parts of lead powder, 0.01-10 parts of MXene material and/or MXene-MAX heterojunction material, 0.1-10 parts of tetrabasic lead sulfate, 3-10 parts of sulfuric acid solution, 0-2 parts of fiber material and 5-20 parts of water.
The preparation method comprises the following steps: mixing lead powder, MXene materials and/or MXene-MAX heterojunction materials, tetrabasic lead sulfate and fiber materials to obtain a dry material mixture; adding water and a sulfuric acid solution into the dry material mixture, stirring and mixing to obtain a wet material mixture; and (4) standing and curing the wet material mixture to obtain the composite positive lead plaster.
In a more specific embodiment, the steps include:
1. the preparation method of the dry auxiliary materials comprises the following steps: uniformly mixing MXene materials and/or MXene-MAX heterojunction materials, tetrabasic lead sulfate and fiber materials in advance to prepare dry auxiliary materials;
2. dry mixing: dry-mixing the prepared dry auxiliary materials with lead powder until the materials are uniformly mixed;
3. wet mixing: adding deionized water into the mixture of the dry auxiliary materials and the lead powder obtained in the step 2, and stirring and wet mixing to obtain slurry;
4. acid mixing step: adding dilute sulfuric acid into the slurry after wet mixing, and carrying out acid mixing; preferably, the acid mixing time is 10-20 min;
5. and (3) curing: and cooling and solidifying the slurry after the acid mixing to obtain the anode lead paste.
Coating the obtained positive lead plaster on a metal grid and in the gap, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
Example 2
This embodiment provides a specific implementation manner of a positive electrode lead paste and a preparation method thereof, wherein an MXene material is Ti with an accordion shape 3 C 2 F x The mass percentage concentration of the sulfuric acid solution is 50 percent; FIG. 3 shows an accordion-like Ti 3 C 2 F x XRD pattern (a) and SEM photograph (b) of (A).
In this embodiment, the positive electrode lead paste includes the following raw materials in parts by weight: 5-8 parts of sulfuric acid solution, 7-16 parts of dry auxiliary materials,8-12 parts of deionized water and 80 parts of lead powder; wherein the dry auxiliary material is Ti 3 C 2 F x 1-10 parts of tetrabasic lead sulfate and 6 parts of tetrabasic lead sulfate.
The specific implementation steps of the preparation of the positive lead paste comprise:
1. according to the weight portion, Ti 3 C 2 F x Mixing with tetrabasic lead sulfate, uniformly mixing, and performing ball milling to obtain dry auxiliary materials;
2. dry mixing the prepared dry auxiliary materials with lead powder, slowly adding the lead powder while stirring, and performing dry mixing for 7 min;
3. adding deionized water into the mixture of the dry auxiliary materials and the lead powder obtained in the step 2, accelerating the stirring speed, continuing stirring for 10min, and uniformly stirring the slurry;
4. adding a sulfuric acid solution into the slurry after wet mixing, carrying out acid mixing and stirring for 10-20 min, and heating to 80 ℃ in the stirring process;
5. and cooling and solidifying the slurry after the acid mixing to below 45 ℃ to obtain the positive lead paste.
And coating the obtained positive lead plaster on a metal grid, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
In a preferred embodiment, the positive electrode lead paste comprises the following raw materials in parts by weight: 6 parts of sulfuric acid solution, 8 parts of dry auxiliary materials, 9 parts of deionized water and 80 parts of lead powder; wherein the dry auxiliary material is Ti 3 C 2 F x 2 parts and 6 parts of tetrabasic lead sulfate. And coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at a high temperature and drying to prepare the positive electrode of the lead-acid battery.
Example 3
This example provides another specific implementation of the positive electrode lead paste and the preparation method thereof, which is similar to example 2, except that the MXene material is Ti with a two-dimensional morphology 3 C 2 F x . FIG. 4 shows a two-dimensional shape MXene material Ti 3 C 2 F x XRD spectrum (a) and SEM photograph (b) of (A). The MXene with the two-dimensional morphology is obtained by peeling MXene material with the accordion morphology (such as ultrasonic)Has obvious two-dimensional lamellar structure.
In a preferred embodiment, the following raw materials are included: 6.3 parts of sulfuric acid solution, 7.8 parts of dry auxiliary materials, 10 parts of deionized water and 76.9 parts of lead powder; wherein the dry auxiliary material is Ti 3 C 2 F x 0.7 portion and 7.1 portions of tetrabasic lead sulfate. The specific implementation procedure for the preparation of positive electrode lead paste was the same as in example 2. Coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
Example 4
This example provides another specific implementation of the positive electrode lead paste and the preparation method thereof, which is similar to example 2, except that the MXene material is Ti with a two-dimensional morphology 3 CNF x 。
In a preferred embodiment, the following raw materials are included: 7 parts of sulfuric acid solution, 9 parts of dry auxiliary materials, 8 parts of deionized water and 76 parts of lead powder; wherein the dry auxiliary material is Ti 3 CNF x 8 parts of tetrabasic lead sulfate and 1 part of tetrabasic lead sulfate. The specific implementation steps for preparing the composite positive electrode lead paste are the same as those in example 2. And coating the obtained composite positive lead plaster on a lead-nickel metal grid and in the gap to prepare the positive electrode of the lead-acid battery.
In general, a fiber material (generally, a conductive fiber) is added to the positive electrode lead paste to improve the conductivity on one hand and increase the strength of the cured positive electrode on the other hand. The MXene material also has an ultrathin two-dimensional structure, and can replace or partially replace the function of a fiber material as an additive.
In addition, the MXene material with a two-dimensional structure is added into the positive electrode of the lead-acid battery to form an effective conductive path in the positive electrode, so that active substances under surface lead sulfate can also react with electrolyte, and the sulfate ratio of the active substances converted into the MXene material is obviously improved in the charging process, thereby improving the utilization rate of the active substances of the negative electrode and prolonging the service life of the lead-acid battery.
Example 5
This example provides another specific implementation of composite positive lead paste and its preparation method,similar to example 2, except that MXene-MAX heterojunction material MXene-Ti was added 3 AlC 2 FIG. 5 shows a MAX phase material Ti 3 AlC 2 (a) And MXene-MAX heterojunction material MXene-Ti 3 AlC 2 (b) Can see MXene-Ti in the SEM photograph 3 AlC 2 The surface is significantly rougher than the MAX phase material. The rough surface is derived from the open accordion shape generated by partial etching, which enables MXene-Ti 3 AlC 2 Not only retains the affinity characteristic of MXene material surface with lead powder and aqueous solution, but also has the excellent corrosion resistance of MAX phase material, namely MXene-Ti 3 AlC 2 The lead-acid battery positive electrode paste is easier to disperse in the positive electrode lead paste, the positive electrode lead paste is also easier to embed into the accordion opening, better material cohesiveness is shown, the problem that the positive electrode of the lead-acid battery is easy to soften and fall off is solved, and the service life and the rate capability of the lead-acid battery are improved.
In order to illustrate the use effect of the MXene material and the MXene-MAX heterojunction material in the lead-acid battery, the positive electrode lead paste in the embodiment is composed of the following raw materials in parts by weight: 8 parts of sulfuric acid solution, 7.2 parts of dry auxiliary materials, 10 parts of deionized water and 80 parts of lead powder; wherein the dry auxiliary material is MXene-Ti 3 AlC 2 5 parts of fiber material, 0.2 part of tetrabasic lead sulfate and 2 parts of sodium sulfate. The specific implementation procedure for the preparation of positive electrode lead paste was the same as in example 2. Coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery. MXene-Ti is prepared by mixing 3 AlC 2 Respectively replaced by MXene material Ti 3 C 2 F x And conductive carbon black to obtain a positive electrode, and the three positive electrodes are assembled into a lead-acid battery to carry out electrochemical performance tests, wherein the results are shown in the following table 1:
TABLE 1 electrochemical performance test results for lead-acid battery anodes with different additives
As can be seen, the internal resistance, capacity, low-temperature performance and cycle performance of the battery added with the MXene material and the MXene-MAX heterojunction material are all better than those of a comparative battery, particularly the MXene-MAX heterojunction material, in electrochemical performance including capacity, low-temperature performance and cycle life.
Example 6
This example provides another specific implementation of positive electrode lead paste and its preparation method, similar to example 5, except that MXene-Ti as MXene-MAX heterojunction material is added 3 SiC 2 。
In this embodiment, the positive electrode lead paste is composed of the following raw materials in parts by weight: 8 parts of sulfuric acid solution, 10 parts of dry auxiliary materials, 10 parts of deionized water and 50 parts of lead powder; wherein the dry auxiliary material is MXene-Ti 3 SiC 2 20 parts of tetrabasic lead sulfate and 5 parts of tetrabasic lead sulfate. The specific implementation procedure for the preparation of positive electrode lead paste was the same as in example 2. Coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
Example 7
This example provides another specific implementation of positive electrode lead paste and its preparation method, similar to example 5, except that MXene-Ti as MXene-MAX heterojunction material is added 3 SnC 2
In this embodiment, the positive electrode lead paste is composed of the following raw materials in parts by weight: 4 parts of sulfuric acid solution, 5.5 parts of dry auxiliary materials, 10 parts of deionized water and 90 parts of lead powder; wherein the dry auxiliary material is MXene-Ti 3 SnC 2 0.5 portion and 5 portions of tetrabasic lead sulfate. The specific implementation procedure for the preparation of positive electrode lead paste was the same as in example 2. Coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
Compared with the MAX phase material of which the component A is Al, the MAX phase material of which the component A is Sn and Si based on the MAX phase material has better corrosion resistance and oxidation resistance, so that MXene-MAX heterojunction materials of which the component A is Sn and Si are preferred in the positive electrode lead paste; more preferably, MXene-MAX heterojunction material with Sn as component A.
Example 8
This example provides another specific implementation of the positive electrode lead paste and the preparation method thereof, similar to example 8, except that the MXene-MAX heterojunction material is MXene-Ta 3 AlC 2 A heterojunction material.
In this embodiment, the positive electrode lead paste is composed of the following raw materials in parts by weight: 8 parts of sulfuric acid solution, 25 parts of dry auxiliary materials, 9.6 parts of deionized water and 60 parts of lead powder; wherein the dry auxiliary material is MXene-Ta 3 AlC 2 10 parts of tetrabasic lead sulfate and 5 parts of tetrabasic lead sulfate. The specific implementation procedure for the preparation of positive electrode lead paste was the same as in example 2. Coating the obtained positive lead plaster on a lead-nickel metal grid frame and in gaps, and curing at high temperature and drying to prepare the positive electrode of the lead-acid battery.
Example 9
The embodiment provides another specific implementation manner of the anode lead paste and the preparation method thereof, wherein an MXene material and an MXene-MAX heterojunction material are added, that is, the MXene material and the MXene-MAX heterojunction material in the additive are used together, and a network is formed in the anode by utilizing the two-dimensional characteristics of the MXene material, so that the conductivity and the stability of the anode are improved, and better electrochemical properties including cycle performance and rate performance are further represented; optionally, the mass ratio of the MXene material to the MXene-MAX heterojunction material can be (0.1-10): 1, adjustment is performed.
In this embodiment, the MXene material is Ti 3 C 2 F x MXene-Ti is selected as MXene-MAX heterojunction material 3 SnC 2 . The positive lead plaster comprises the following raw materials in parts by weight: 8 parts of sulfuric acid solution, 4.5 parts of dry auxiliary materials, 9.3 parts of deionized water and 80 parts of lead powder; wherein the dry auxiliary material is Ti 3 C 2 F x 0.5 part of MXene-Ti 3 SnC 2 2 parts and 2 parts of tetrabasic lead sulfate.
Example 10
This example provides another specific implementation of the positive electrode lead paste and the preparation method thereof, which is similar to example 8, except that the MXene material is Mo with a two-dimensional morphology 2 CF x MXene-MAX heterojunction materialMXene-Ti is selected 3 SiC 2 。
In the embodiment, the composite positive lead paste is composed of the following raw materials in parts by weight: 5 parts of sulfuric acid solution, 15 parts of dry auxiliary materials, 10 parts of deionized water and 60 parts of lead powder; wherein the dry auxiliary material is Ti 3 C 2 F x 5 parts of MXene-Ti 3 SiC 2 5 parts of tetrabasic lead sulfate and 5 parts of tetrabasic lead sulfate. And coating the obtained positive lead plaster on a lead-nickel metal grid and in the gap to prepare the positive electrode of the lead-acid battery.
Example 11
This example provides another specific implementation of a positive electrode lead paste and a method for preparing the same, which is similar to example 8, except that the positive electrode lead paste includes an MXene material and a MAX phase material, and the MXene material is Ti with a two-dimensional morphology 2 CF x The MAX phase material is Ti 3 SnC 2 The two-dimensional structure characteristic of MXene material and the characteristic of MAX phase material of excellent conductivity and corrosion resistance are utilized.
In the embodiment, the composite positive lead paste is composed of the following raw materials in parts by weight: 5 parts of sulfuric acid solution, 10 parts of dry auxiliary materials, 10 parts of deionized water and 70 parts of lead powder; wherein the dry auxiliary material is Ti 2 CF x 0.5 part of Ti 3 SnC 2 5 parts of tetrabasic lead sulfate and 4.5 parts of tetrabasic lead sulfate. And coating the obtained positive lead plaster on a lead-nickel metal grid and in the gap to prepare the positive electrode of the lead-acid battery.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The positive pole lead paste of the lead-acid battery is characterized by comprising an MXene material and/or an MXene-MAX heterojunction material.
2. The positive electrode lead paste according to claim 1, wherein the MXene material has a chemical formula of M n+1 X n T x Wherein M is selected from one or more transition metal elements, X is selected from one or more carbon, nitrogen or boron elements, T x Represents a functional group including-F, -Cl, Br, I, -O, -S, -OH, -NH 4 N is more than or equal to 1 and less than or equal to 4; preferably, the M is selected from at least one of Ti, V, Mo, Nb, Ta, W and Cr;
and/or the chemical formula of the MXene-MAX heterojunction material is represented as M n+1 X n -M n+1 AX n Wherein M is selected from one or more transition metal elements, A is selected from elements of a third main group and/or a fourth main group, X is selected from one or more carbon, nitrogen or boron elements, and n is more than or equal to 1 and less than or equal to 4; preferably, the M is selected from at least one of Ti, V, Mo, Nb, Ta, W and Cr, and the A is selected from Al, Sn or Si elements;
and/or the mass percentage of the MXene material and/or the MXene-MAX heterojunction material in the dry material of the positive electrode lead paste is 0.1-80%.
And/or the positive electrode lead paste also contains MAX phase materials.
3. The positive electrode lead paste according to claim 1 or 2, wherein the positive electrode lead paste comprises, in parts by weight:
50-90 parts of lead powder and/or lead-containing compound powder;
0.01 to 50 parts of MXene material and/or MXene-MAX heterojunction material.
Wherein the lead-containing compound comprises one or more of basic lead sulfate, lead oxide and red lead.
4. A method for preparing positive electrode lead paste according to any one of claims 1 to 3, characterized by comprising the steps of:
mixing lead powder or lead-containing compound powder, MXene material and/or MXene-MAX heterojunction material to obtain dry material mixture;
adding water and a sulfuric acid solution into the dry material mixture, and stirring and mixing to obtain a wet material mixture;
and standing and curing the wet material mixture to obtain the composite positive lead plaster.
5. Use of an MXene material and/or an MXene-MAX heterojunction material as a positive electrode additive for a lead acid battery.
6. The lead-acid battery positive electrode is characterized by comprising an MXene material and/or an MXene-MAX heterojunction material.
7. A method for preparing the positive electrode of the lead-acid battery according to claim 6, characterized in that the positive electrode lead paste according to any one of claims 1 to 3; or, coating the positive lead plaster obtained by the preparation method of claim 4 on a grid to prepare the lead-acid battery positive electrode.
8. A lead-acid battery comprising the positive electrode for a lead-acid battery according to claim 6; or, the lead-acid battery positive electrode obtained by the preparation method according to claim 7.
9. An electric vehicle comprising the lead-acid battery of claim 9.
10. A vehicle comprising the lead-acid battery of claim 9.
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