CN114975895B - Positive electrode lead paste of lead-acid battery, positive electrode, preparation method of positive electrode, battery and electric vehicle - Google Patents
Positive electrode lead paste of lead-acid battery, positive electrode, preparation method of positive electrode, battery and electric vehicle 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
- H01M4/14—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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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
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- 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
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- H01M4/14—Electrodes for lead-acid accumulators
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Abstract
The application discloses a positive electrode lead paste of a lead-acid battery, a positive electrode, a preparation method thereof, a battery and an electric vehicle, wherein the positive electrode lead paste contains an MXene material and/or an MXene-MAX heterojunction material.
Description
Technical Field
The application belongs to the technical field of lead-acid batteries, and particularly relates to positive electrode lead paste and positive electrode of a lead-acid battery, a preparation method of the positive electrode lead paste and the positive electrode, a 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, wider applicable temperature range, safety and reliability compared with a lithium battery and the like, the lead-acid battery is still a secondary battery with larger share and the widest applicable range in the battery market, and particularly in 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 is ranked first in the world.
The lead-acid storage battery negative electrode 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 the positive plate PbO is normalized 2 The content is still low, the resistance of the positive electrode active material is large, and the low-temperature performance and the power characteristic of the battery are obviously affected. And the coverage effect of the lead sulfate of the discharge product and the conductivity of the 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. To improve the electrochemical performance of the positive electrode of a lead-acid battery, a large amount of conductive agents, such as graphite, graphene, carbon fiber and other carbon-containing components, are generally added during paste mixing, and the addition of the conductive agents 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 agents are oxidized into carbon dioxide in the initial period of circulation, the structural strength of active substances is reduced, and the service life of the battery is shortened. At the same time, some ceramic conductive additives such as SnO 2 、Ti 4 O 7 、BaPbO 3 The lead-acid battery has large volume change of lead dioxide and lead sulfate in charge and discharge cycles due to uncontrollable morphology and smooth particles>90 percent) leads to easy softening and falling of positive electrode active substances, resulting in the decrease of the strength of a positive electrode plate of the battery and leading to the failure of the lead-acid battery in advance of the mud falling of lead plaster.
Disclosure of Invention
Aiming at the problems of the positive electrode of the lead-acid battery, the application provides a novel conductive two-dimensional material MXene material and/or MXene-MAX heterojunction material which are used as a conductive agent, and positive electrode lead paste of the lead-acid battery 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 an electrode and improve the circulation stability and the multiplying power performance of the lead-acid battery.
The first aspect of the application provides a positive electrode lead plaster of a lead-acid battery, which contains an MXene material and/or an MXene-MAX heterojunction material.
In some embodiments, the chemical formula of the MXene material described above is represented by M n+1 X n T x Wherein M is selected from one or more of transition metal elements, X is selected from one or more of carbon, nitrogen or boron elements, T x Represents a functional group of the polymer, comprising-F, -Cl, br, I, -O, -S, -OH, -NH 4 One or more ofN 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, 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 of 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 of 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, cr; the A is selected from Al, sn or Si.
In some embodiments, the mass percentage of the dry material in the positive electrode lead paste of the MXene material and/or the MXene-MAX heterojunction material 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 the following components 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 above lead-containing compound powder includes: one or more of basic lead sulfate, lead oxide and red lead.
The second aspect of the application provides a preparation method of positive lead plaster, comprising the following steps: mixing lead powder or lead-containing compound powder, an MXene material and/or an MXene-MAX heterojunction material to obtain a dry material mixture; adding water and sulfuric acid solution into the dry material mixture, stirring and mixing to obtain a wet material mixture; and (3) placing and curing the wet mixture to obtain the composite positive lead plaster.
In a third aspect the application provides the use of an MXene material and/or an MXene-MAX heterojunction material as a positive electrode additive for a lead acid battery.
In a fourth aspect, the application provides a positive electrode for a lead acid battery comprising an MXene material and/or an MXene-MAX heterojunction material.
The fifth aspect of the application provides a method for preparing the positive electrode of the lead-acid battery, which is characterized in that the positive electrode lead paste is prepared; or the positive electrode lead plaster obtained by the preparation method is coated on a grid to prepare the positive electrode of the lead-acid battery.
A sixth aspect of the present application provides a lead acid battery comprising the positive electrode of a lead acid battery described above; or the positive electrode of the lead-acid battery obtained by the preparation method.
A seventh aspect of the present application provides an electric vehicle comprising the lead-acid battery described above.
An eighth aspect of the application provides a vehicle comprising a lead acid battery as described above.
The application provides an application of an MXene material and/or an MXene-MAX heterojunction material in a positive electrode of a lead-acid battery as an additive, and the excellent technical effects are as follows:
1. the MXene material and/or the MXene-MAX heterojunction material have excellent conductivity, and the conductivity of the positive electrode material can be effectively improved by being 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 multiplying power performance and the cycling stability of lead acid can be improved;
2. the MXene material and/or the MXene-MAX heterojunction material have excellent corrosion resistance and oxidation resistance, are not easy to oxidize and corrode in the positive electrode material of the lead-acid battery and in the environment of sulfuric acid electrolyte, can improve the conductivity of the lead-acid battery, can also ensure the stability of the positive electrode of the lead-acid battery, and avoid the permanent loss of battery energy density and cycle life caused by the oxidation and corrosion of the positive electrode of the lead-acid battery.
3. The MXene material and/or the MXene-MAX heterojunction material provided by the application has a high specific surface area, the contact area between the MXene material and the lead-acid battery anode is increased, and especially the MXene-MAX heterojunction material has an open accordion shape, so that the lead-acid battery anode can be more dispersed and separated, the problem that the lead-acid battery anode is easy to soften and fall off is solved, and the service life and the multiplying power performance of the lead-acid battery are improved.
Drawings
FIG. 1 is a schematic diagram of the relationship of the preparation process of MAX phase material, MXene-MAX heterojunction material and MXene material in the present application;
FIG. 2 shows the MAX phase material Ti in the application 3 AlC 2 A high resolution electron microscope photograph of (a) and a lattice spacing analysis photograph of (b); high resolution electron microscope pictures of MXene-MAX heterojunction materials, a structural schematic diagram (c) and lattice spacing analysis pictures (d);
FIG. 3 is an accordion-like MXene material Ti according to example 2 of the present application 3 C 2 F x XRD patterns (a) and SEM pictures (b);
FIG. 4 is a two-dimensional morphology of MXene material Ti in example 3 of the application 3 C 2 F x XRD patterns (a) and SEM pictures (b);
FIG. 5 is a MAX phase material Ti in example 5 of the application 3 AlC 2 (a) And MXene-Ti 3 AlC 2 SEM photograph of heterojunction material (b).
Detailed Description
The technical scheme of the application is described below through specific examples. It is to be understood that the reference to one or more steps of the application does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application, which relative changes or modifications may be regarded as the scope of the application which may be practiced without substantial technical content modification.
The MXene material, MXene-MAX heterojunction material and MAX phase material used in the examples were purchased from beijing tricyclopedia energy science and technology, other raw materials and instruments, and their sources were not particularly limited, and they were purchased in the market or prepared according to conventional methods well known to those skilled in the art.
The MXene phase material is obtained by etching the A component in the MAX phase material, and the surface of the MXene phase material has the characteristics of the accordion MXene material and the inside of the MXene phase material is provided withMaterials featuring MAX phase materials are similar to MXene-MAX heterojunction materials of "sea urchin" structure. The material preparation process is schematically shown in figure 1. We use Ti as 3 AlC 2 By way of example, the characteristics of such a MXene-MAX heterojunction material are illustrated in FIG. 2, where FIGS. 2a and b illustrate the MAX phase material Ti 3 AlC 2 A high resolution electron microscope photograph of (a) and a lattice spacing analysis photograph of (b); FIGS. 2c and d present Ti 3 AlC 2 Partially etched MXene-MAX heterojunction material (denoted as MXene-Ti 3 AlC 2 ) High resolution electron microscope photograph of (C) and its structural schematic drawing and lattice spacing analysis photograph (d), and MXene-Ti can be seen by comparison 3 AlC 2 Is obviously different from Ti in surface morphology 3 AlC 2 The surface exhibits the characteristics of MXene.
Example 1
The embodiment provides a positive electrode lead plaster and a preparation method thereof, wherein the positive electrode lead plaster comprises the following components in parts by weight: 50 to 90 parts of lead powder, 0.01 to 50 parts of MXene material and/or MXene-MAX heterojunction material, 0.1 to 20 parts of tetrabasic lead sulfate, 3 to 15 parts of sulfuric acid solution, 0 to 2 parts of fiber material and 5 to 20 parts of water.
In a preferred embodiment, the positive electrode lead plaster comprises the following components 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 plaster comprises, 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, an MXene material and/or an MXene-MAX heterojunction material, tetrabasic lead sulfate and a fiber material to obtain a dry material mixture; adding water and sulfuric acid solution into the dry material mixture, stirring and mixing to obtain a wet material mixture; and (3) placing and curing the wet mixture to obtain the composite positive lead plaster.
In a more specific embodiment, the steps include:
1. the preparation of dry auxiliary materials comprises the following steps: uniformly mixing an MXene material and/or an MXene-MAX heterojunction material, tetrabasic lead sulfate and a fiber material in advance to prepare a dry auxiliary material;
2. and (3) dry mixing: dry-mixing the prepared dry auxiliary materials and lead powder until the dry auxiliary materials and the lead powder 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: adding dilute sulfuric acid into the wet mixed slurry, and carrying out acid mixing; preferably, the acid mixing time is between 10 and 20 minutes;
5. and (3) curing: and cooling and solidifying the slurry after the acid mixing to obtain the positive lead plaster.
And coating the obtained positive lead plaster on a metal grid frame and in a gap, and performing high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
Example 2
The embodiment provides a concrete implementation mode of a positive electrode lead plaster and a preparation method thereof, wherein an MXene material is Ti with accordion shape 3 C 2 F x The mass percentage concentration of the sulfuric acid solution is 50%; FIG. 3 shows an accordion-like Ti 3 C 2 F x XRD pattern (a) and SEM photograph (b).
In the embodiment, the positive electrode lead plaster comprises 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 made of Ti 3 C 2 F x 1-10 parts and 6 parts of tetrabasic lead sulfate.
The specific implementation steps of the preparation of the positive lead plaster comprise:
1. according to parts by weight, ti 3 C 2 F x Mixing with tetrabasic lead sulfate, and ball milling to obtain dry auxiliary materials;
2. dry-mixing the prepared dry auxiliary material and lead powder, slowly adding the lead powder while stirring, and dry-mixing for 7min;
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 sulfuric acid solution into the wet mixed slurry, 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 electrode lead plaster.
And coating the obtained positive electrode lead paste on a metal grid frame, and performing high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
In a preferred embodiment, the positive electrode lead plaster 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 made of Ti 3 C 2 F x 2 parts and 6 parts of tetrabasic lead sulfate. And coating the obtained positive electrode lead plaster on the lead nickel metal grid frame and in the gaps, and carrying out high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
Example 3
The present example provides another embodiment of the positive electrode lead paste and the method for preparing the same, similar to example 2, except that the MXene material is Ti with two-dimensional morphology 3 C 2 F x . FIG. 4 shows a two-dimensional morphology of the MXene material Ti 3 C 2 F x XRD patterns (a) and SEM pictures (b). The two-dimensional MXene is obtained by stripping (such as ultrasonic) an accordion-shaped MXene material, and has an obvious two-dimensional lamellar structure.
In a preferred embodiment, the following 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 made of Ti 3 C 2 F x 0.7 parts and 7.1 parts of tetrabasic lead sulfate. The procedure for preparing the positive electrode lead paste was the same as in example 2. And coating the obtained positive electrode lead plaster on the lead nickel metal grid frame and in the gaps, and carrying out high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
Example 4
The present embodiment provides anotherThe specific embodiment of the anode lead paste and the preparation method thereof is similar to example 2, except that the MXene material is Ti with two-dimensional morphology 3 CNF x 。
In a preferred embodiment, the following 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 made of Ti 3 CNF x 8 parts of tetrabasic lead sulfate and 1 part of tetrabasic lead sulfate. The specific implementation procedure for preparing the composite positive electrode lead plaster is the same as in example 2. And coating the obtained composite positive electrode lead plaster on the lead nickel metal grid frame and in the gaps to prepare the positive electrode of the lead-acid battery.
In general, a fibrous material (generally, conductive fiber) is added to the positive electrode lead paste, which is used for improving conductivity and strength of the cured positive electrode. The MXene material also has an ultra-thin two-dimensional structure that can also be used as an additive to replace or partially replace the fibrous material.
In addition, the two-dimensional structure of the MXene material can form an effective conductive path in the positive electrode of the lead-acid battery, so that active substances under the surface lead sulfate can react with electrolyte, and the sulfate ratio of the active substances can be obviously improved in the charging process, thereby improving the utilization rate of the negative electrode active substances and prolonging the service life of the lead-acid battery.
Example 5
The present example provides another embodiment of a composite positive lead paste and method of making the same, similar to example 2, except that MXene-MAX heterojunction material MXene-Ti is added 3 AlC 2 FIG. 5 shows the MAX phase material Ti 3 AlC 2 (a) And MXene-MAX heterojunction material MXene-Ti 3 AlC 2 (b) SEM photograph of (C) and (D) can be seen in MXene-Ti 3 AlC 2 The surface is significantly rougher than the MAX phase material. This roughened surface results from the open accordion morphology created by the partial etch, which causes MXene-Ti 3 AlC 2 Not only maintains the affinity characteristic of the surface of the MXene material with lead powder and aqueous solution, but also has excellent corrosion resistance of MAX phase material, and MXene-Ti 3 AlC 2 The lead-acid battery positive electrode is easier to disperse in the positive electrode lead paste, the positive electrode lead paste is also easy to embed into an accordion opening, the better material cohesiveness is represented, 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 multiplying power performance of the lead-acid battery are improved.
In order to illustrate the use effect of the lead-acid battery made of the MXene material and the MXene-MAX heterojunction material, the positive electrode lead plaster in the embodiment comprises 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 composed of MXene-Ti 3 AlC 2 5 parts of fibrous material 0.2 parts and 2 parts of tetrabasic lead sulfate. The procedure for preparing the positive electrode lead paste was the same as in example 2. And coating the obtained positive electrode lead plaster on the lead nickel metal grid frame and in the gaps, and carrying out high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery. Will use the same formulation, MXene-Ti 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 electrode assembled lead-acid batteries were subjected to electrochemical performance tests, the results of which are shown in the following table 1:
TABLE 1 electrochemical performance test results of the positive electrodes of lead acid batteries with different additives
It can be seen that the internal resistance, capacity, low temperature performance and cycle performance of the battery with the addition of the MXene material and the MXene-MAX heterojunction material are all based on the comparison sample battery, and the MXene-MAX heterojunction material in particular shows the optimal electrochemical performance, including capacity, low temperature performance and cycle life.
Example 6
This example provides another embodiment of a positive lead paste and method of making the same, similar to example 5, except that MXene-MAX heterojunction material MXene-Ti is added 3 SiC 2 。
In the embodiment, the positive electrode lead plaster comprises the following raw materials in parts by weight: sulfur (S)8 parts of 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 composed of MXene-Ti 3 SiC 2 20 parts of tetrabasic lead sulfate and 5 parts of tetrabasic lead sulfate. The procedure for preparing the positive electrode lead paste was the same as in example 2. And coating the obtained positive electrode lead plaster on the lead nickel metal grid frame and in the gaps, and carrying out high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
Example 7
This example provides another embodiment of a positive lead paste and method of making the same, similar to example 5, except that MXene-MAX heterojunction material MXene-Ti is added 3 SnC 2
In the embodiment, the positive electrode lead plaster comprises 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 composed of MXene-Ti 3 SnC 2 0.5 part and 5 parts of tetrabasic lead sulfate. The procedure for preparing the positive electrode lead paste was the same as in example 2. And coating the obtained positive electrode lead plaster on the lead nickel metal grid frame and in the gaps, and carrying out high-temperature curing and drying treatment to prepare the positive electrode of the lead-acid battery.
MAX phase materials based on Sn and Si as a component in the MAX phase material exhibit better corrosion resistance and oxidation resistance than MAX phase materials based on Al as a component, so MXene-MAX heterojunction materials with Sn and Si as a component are preferred in positive electrode lead pastes; more preferably, is an MXene-MAX heterojunction material with an A component of Sn.
Example 8
This example provides another embodiment of a positive lead paste and method of making the same, similar to example 8, except that the MXene-MAX heterojunction material is MXene-Ta 3 AlC 2 Heterojunction materials.
In the embodiment, the positive electrode lead plaster comprises 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 procedure for preparing the positive electrode lead paste was the same as in example 2. To be obtainedThe positive lead plaster is coated on the lead nickel metal grid frame and in the gaps, and the positive lead plaster is prepared into the positive electrode of the lead-acid battery through high-temperature curing and drying treatment.
Example 9
The embodiment provides another specific implementation mode of the positive electrode lead plaster and the preparation method thereof, wherein an MXene material and an MXene-MAX heterojunction material are added, namely the MXene material and the MXene-MAX heterojunction material are used together in the additive, and a network is formed in the positive electrode by utilizing the two-dimensional characteristic of the MXene material, so that the conductivity and the stability of the positive electrode are improved, and better electrochemical performances including cycle performance and multiplying power performance are further shown; alternatively, the mass ratio of the MXene material to the MXene-MAX heterojunction material may be between (0.1-10): 1, performing adjustment.
In this embodiment, the MXene material is selected from Ti 3 C 2 F x The MXene-MAX heterojunction material is selected from MXene-Ti 3 SnC 2 . The positive lead plaster consists of 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 made of Ti 3 C 2 F x 0.5 part of MXene-Ti 3 SnC 2 2 parts of tetrabasic lead sulfate and 2 parts of tetrabasic lead sulfate.
Example 10
The present example provides another embodiment of the positive electrode lead paste and the method for preparing the same, similar to example 8, except that the MXene material is Mo of two-dimensional morphology 2 CF x The MXene-MAX heterojunction material is selected from MXene-Ti 3 SiC 2 。
In the embodiment, the composite positive electrode lead plaster comprises 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 made of 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 electrode lead plaster on the lead-nickel metal grid frame and in the gaps to prepare the positive electrode of the lead-acid battery.
Example 11
The present embodiment provides another positive electrode leadThe paste and the preparation method thereof are similar to those of example 8, except that the paste comprises an MXene material and a MAX phase material, wherein the MXene material adopts Ti with two-dimensional morphology 2 CF x The MAX phase material is Ti 3 SnC 2 The two-dimensional structure characteristic of the MXene material and the MAX phase material have excellent conductivity and corrosion resistance.
In the embodiment, the composite positive electrode lead plaster comprises 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 made of 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 electrode lead plaster on the lead-nickel metal grid frame and in the gaps to prepare the positive electrode of the lead-acid battery.
The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application 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 the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.
Claims (23)
1. The preparation method of the positive electrode lead plaster of the lead-acid battery is characterized by comprising the following steps:
mixing lead powder or lead-containing compound powder, an MXene material and/or an MXene-MAX heterojunction material to obtain a dry material mixture;
adding water and sulfuric acid solution into the dry material mixture, stirring and mixing to obtain a wet material mixture;
and (3) placing and curing the wet mixture to obtain the composite positive lead plaster.
2. The method for preparing the lead-acid battery anode lead plaster according to claim 1,characterized in that the chemical formula of the MXene material is expressed as M n+1 X n T x Wherein M is selected from one or more of transition metal elements, X is selected from one or more of carbon, nitrogen or boron elements, and T represents a functional group comprising-F, -Cl, br, I, -O, -S, -OH, NH 4 N is more than or equal to 1 and less than or equal to 4;
and/or the chemical formula of the MXene-MAX heterojunction material is expressed as M n+1 X n -M n+1 AX n Wherein M is selected from one or more of 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 of carbon, nitrogen or boron elements, and n is more than or equal to 1 and less than or equal to 4;
and/or the mass percentage of the dry materials of the MXene material and/or the MXene-MAX heterojunction material in the positive lead paste is between 0.1 and 80 percent;
and/or, the positive electrode lead plaster also contains MAX phase materials.
3. The method for preparing the positive lead plaster for the lead-acid battery according to claim 2, wherein the M in the chemical formula of the MXene material is at least one selected from Ti, V, mo, nb, ta, W, cr;
and/or, the M in the chemical formula of the MXene-MAX heterojunction material is selected from at least one of Ti, V, mo, nb, ta, W, cr, and the A is selected from Al, sn or Si elements.
4. The method for preparing the positive electrode lead plaster of the lead-acid battery according to any one of claims 1 to 3, wherein the positive electrode lead plaster comprises the following components 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.
5. A lead-acid battery positive electrode lead paste obtained by the production method according to any one of claims 1 to 4.
6. The positive electrode lead paste of the lead-acid battery is characterized by comprising an MXene-MAX heterojunction material.
7. The lead-acid battery positive electrode lead paste according to claim 6, wherein 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 of 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 of carbon, nitrogen or boron elements, and n is more than or equal to 1 and less than or equal to 4.
8. The lead-acid battery positive electrode lead paste of claim 7, wherein the M in the chemical formula of the MXene-MAX heterojunction material is selected from at least one of Ti, V, mo, nb, ta, W, cr and the a is selected from Al, sn, or Si element.
9. The lead-acid battery positive electrode lead paste according to claim 6, wherein the mass percentage of dry materials in the positive electrode lead paste of the MXene-MAX heterojunction material is between 0.1 and 80 percent.
10. The lead acid battery positive electrode lead paste of claim 6, further comprising an MXene material.
11. The lead acid battery positive electrode lead paste of claim 10, wherein the MXene material has a chemical formula represented by M n+1 X n T x Wherein M is selected from one or more of transition metal elements, X is selected from one or more of carbon, nitrogen or boron elements, and T represents a functional group comprising-F, -Cl, br, I, -O, -S, -OH, NH 4 N is more than or equal to 1 and less than or equal to 4.
12. The lead-acid battery positive lead paste of claim 11, wherein M is selected from at least one of Ti, V, mo, nb, ta, W, cr.
13. The positive lead-acid battery lead paste according to claim 5 or 10, further comprising a MAX phase material.
14. The lead-acid battery positive electrode lead paste according to claim 10, wherein the mass percentage of dry materials in the positive electrode lead paste of the MXene material and the MXene-MAX heterojunction material is 0.1% -80%.
15. The positive lead-acid battery lead paste according to any one of claims 5 to 12, 14, wherein the positive 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.
16. Use of an MXene-MAX heterojunction material as positive electrode additive for lead acid batteries.
17. A positive electrode additive for a lead acid battery, the positive electrode additive comprising an MXene material and/or an MXene-MAX heterojunction material.
18. The positive electrode of the lead-acid battery is characterized by comprising an MXene-MAX heterojunction material.
19. A method for preparing a positive electrode of a lead-acid battery, which is characterized in that the positive electrode lead paste of the lead-acid battery is prepared by the method according to any one of claims 5 to 15;
or, the lead-acid battery positive electrode lead paste obtained by the preparation method of any one of claims 1 to 4 is coated on a grid to prepare the lead-acid battery positive electrode.
20. A positive electrode of a lead acid battery obtained by the method of manufacture of claim 19.
21. A lead acid battery comprising the positive electrode of the lead acid battery of claim 18 or 20; or, the positive electrode of the lead-acid battery obtained by the preparation method of claim 19.
22. An electric vehicle comprising the lead acid battery of claim 21.
23. A vehicle comprising the lead acid battery of claim 21.
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