CN114976036B - Metal lead composite material and application thereof, lead-acid battery electrode grid and preparation method thereof, electrode, battery and electric vehicle - Google Patents

Metal lead composite material and application thereof, lead-acid battery electrode grid and preparation method thereof, electrode, battery and electric vehicle Download PDF

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CN114976036B
CN114976036B CN202210647272.5A CN202210647272A CN114976036B CN 114976036 B CN114976036 B CN 114976036B CN 202210647272 A CN202210647272 A CN 202210647272A CN 114976036 B CN114976036 B CN 114976036B
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lead
composite material
mxene
additive
metallic
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CN114976036A (en
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杨树斌
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Beihang University
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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
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/68—Selection of materials for use in lead-acid accumulators
    • H01M4/685—Lead alloys
    • 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
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/82—Multi-step processes for manufacturing carriers for lead-acid accumulators
    • H01M4/84—Multi-step processes for manufacturing carriers for lead-acid accumulators involving casting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The application discloses a metal lead composite material and application thereof, a lead-acid battery electrode grid and a preparation method thereof, an electrode, a battery and an electric vehicle, wherein the metal lead composite material comprises metal lead or metal lead alloy, and an additive, and the additive comprises: the MXene material, the MXene-MAX heterojunction material and the MAX phase material have high conductivity, are uniformly dispersed in molten metal lead liquid, and are cooled and solidified to obtain a novel high-conductivity metal lead composite material; the metal lead composite material has excellent corrosion resistance, stability and conductivity in an acidic environment; meanwhile, the mechanical property of the metal lead composite material can be improved, and the metal lead composite material is particularly suitable for electrode grids of lead-acid batteries; compared with the metal lead or the alloy thereof, the metal lead composite material has smaller density, and can effectively reduce the weight of the battery when being used as an electrode grid of the lead-acid battery, thereby improving the energy density of the lead-acid battery.

Description

Metal lead composite material and application thereof, lead-acid battery electrode grid and preparation method thereof, electrode, battery and electric vehicle
Technical Field
The application belongs to the technical field of lead-acid batteries, and particularly relates to a metal lead composite material and application thereof, a lead-acid battery electrode grid and a preparation method thereof, an electrode, a battery and an electric vehicle.
Background
In the current battery market, 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, and is still the secondary battery with the largest share and the widest applicable range in the battery market, in particular 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 is ranked first in the world.
The main disadvantages of the current commercial lead-acid battery are low energy density and short cycle life, one of the main reasons is that the main materials of the electrode grid of the lead-acid battery are pure lead or lead-tin-calcium alloy, etc., and the mass density is larger>10g/cm 3 ) Resulting in a lead acid battery of higher overall mass and energy density typically not exceeding 50Wh/kg. In the second aspect, the grid acts as a current collector in direct contact with the active material, and generally requires higher conductivity to ensure stable charge and discharge cycles of the battery. However, as a current collector of a lead acid battery, since an electrolyte used for the lead acid battery is a sulfuric acid solution, the electrode plate is also required to have a strong corrosion resistance to the sulfuric acid solution. Moreover, when the lead-based grid is in the cycle of the lead-acid battery, if the lead-based grid is not charged in time after discharging but is placed for a long time, or is overcharged during charging, the lead electrode plate reacts with electrolyte, so that the contact area between the electrode plate and active substances is reduced, and the interface contact is poor, so that the charge-discharge cycle of the battery is failed. The corrosion phenomenon, especially of positive grids, is more pronounced, since it operates at high potential (about 2.0V) and is associated with PbO having a strong oxidation product 2 The contact is easy to cause the grid to be easy to oxidize and corrode, break and collapse, and lead-acid battery failure is caused. If the metal with better conductivity is added into the polar plate, the problem of higher chemical activity and easy reaction with the acid electrolyte is solved; if inorganic materials such as oxidation-resistant oxides are added, the conductivity of the grid is deteriorated. In addition, when preparing the lead-based composite material, the molten lead has high surface energy, is not compatible with other elements or materials, so that the material in the grid is unevenly distributed, the mechanical property of the grid is poor, and the normal use of the lead-acid battery after being impacted and the like is influenced. It can be seen that developing a new type of light, corrosion resistant, highly conductive, high strength grid is a great challenge for the development of high performance lead acid batteries.
Disclosure of Invention
The application adds a novel additive into metal lead or metal lead alloy to obtain a novel metal lead composite material, and the metal lead composite material is used for an electrode grid of a lead-acid battery to solve or partially solve the technical problems that the existing additive is difficult to be compatible with lead and the conductivity of the grid is reduced.
In a first aspect of the application, there is provided a metallic lead composite comprising: metallic lead or metallic lead alloy; and, an additive; the additive comprises: at least one of an MXene material, an MXene-MAX heterojunction material and a MAX phase 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 N is more than or equal to 1 and less than or equal to 4.
In some embodiments, M is selected from at least one of Ti, V, mo, nb, ta, W, cr in the chemical formulas of the MXene materials described above.
In some embodiments, the chemical formula of the MAX phase material is represented by 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; n is more than or equal to 1 and less than or equal to 4.
In some embodiments, in the formulas of MAX phase materials described above, M is selected from at least one of Ti, V, mo, nb, ta, W, cr;
in some embodiments, in the chemical formula of the MAX phase material described above, the a is selected from the group consisting of Sn or Si elements.
In some embodiments, the additive is present in an amount of 0.01% to 95% by mass.
In some embodiments, the additive is present in an amount of 0.01% to 80% by mass.
In some embodiments, the additive is present in an amount of 0.01% to 50% by mass.
In some embodiments, the additive is present in an amount of 0.01% to 20% by mass.
In some embodiments, the metallic lead alloy described above includes lead-tin alloy, lead-calcium alloy, lead-tin-calcium alloy, lead-antimony-tin alloy.
In some embodiments, the metallic lead composite material described above has a content of metallic lead element of at least greater than 5wt.%.
In some embodiments, the metallic lead composite material described above has a content of metallic lead element of at least greater than 20wt.%.
In some embodiments, the metallic lead composite material described above has a content of metallic lead element of at least greater than 50wt.%.
In some embodiments, the metallic lead composite material described above has a content of metallic lead element of at least greater than 80wt.%.
In some embodiments, the above additive further comprises: graphite, expanded graphite, graphene, carbon fiber, carbon nanotube, activated carbon, porous carbon, carbon aerogel.
The second aspect of the application provides the use of the metal lead composite material for the electrode grid of a lead-acid battery.
The third aspect of the application provides a method for preparing the metal lead composite material, comprising the following steps: heating and melting metallic lead into lead liquid, adding an additive into the lead liquid, and stirring to obtain mixed lead slurry; and cooling and solidifying the mixed lead slurry to obtain the metal lead composite material.
In a fourth aspect, the present application provides an electrode grid for a lead acid battery, the electrode grid being formed from the metallic lead composite material described above.
The fifth aspect of the present application provides a method for preparing the electrode grid, comprising the steps of: heating and melting metallic lead into lead liquid, adding an additive into the lead liquid, and stirring to obtain mixed lead slurry; injecting the mixed lead paste into an electrode grid die, and cooling and solidifying to obtain an electrode grid; wherein the additive comprises: MXene material and/or MAX phase material.
A sixth aspect of the application provides a lead acid battery electrode comprising: a positive electrode and a negative electrode, wherein the lead-acid battery electrode comprises the electrode grid; or the lead-acid battery electrode contains the electrode grid obtained by the preparation method.
A seventh aspect of the present application is a lead-acid battery comprising the electrode grid described above; or the lead-acid battery comprises the electrode grid obtained by the preparation method.
An eighth aspect of the present application provides an electric vehicle comprising the above lead-acid battery.
A ninth aspect of the application provides a vehicle comprising a lead acid battery as described above.
The beneficial technical effects of the application are as follows:
1. the application discovers that the MXene material, the MXene-MAX heterojunction material and the MAX phase material have phase affinity with molten metal lead liquid or metal lead alloy liquid, can be uniformly dispersed in the molten metal lead liquid or the metal lead alloy liquid, effectively reduce the surface energy of the molten metal lead liquid or the metal lead alloy liquid, is also beneficial to the addition of other materials (graphite, expanded graphite, graphene, carbon fiber, carbon nano tube, activated carbon, porous carbon, carbon aerogel and the like), and further obtains a novel metal lead composite material after cooling and solidifying;
2. the application discovers that the MXene material, the MXene-MAX heterojunction material and the MAX phase material have high conductivity, are uniformly dispersed in molten metal lead liquid, and are cooled and solidified to obtain a novel high-conductivity metal lead composite material;
3. the metal lead composite material has excellent oxidation resistance, corrosion resistance, high stability and high conductivity in an acidic environment; meanwhile, the mechanical property and strength of the metal lead composite material can be improved by adding the MXene material, the MXene-MAX heterojunction material and the MAX phase material, and the metal lead composite material is particularly suitable for electrode grids of lead-acid batteries;
4. compared with the metal lead or the alloy thereof, the metal lead composite material has smaller density, and can reduce the weight of the battery when being used as an electrode grid of the lead-acid battery, thereby improving the mass specific energy and the energy density of the lead-acid battery.
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 a schematic diagram of an accordion-like MXene material Ti according to example 2 of the present application 3 C 2 F x XRD (a) and SEM photograph (b);
FIG. 4 is a photograph of a mixed lead slurry obtained by adding 5% (a) and 30% (b) of an MXene material to a molten lead bath in example 2 of the present application;
FIG. 5 is a photograph of molten lead solution added graphene as given in example 2 of the present application;
FIG. 6 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. 7 shows the MAX phase material Ti in example 5 of the present application 3 AlC 2 XRD patterns (a) and SEM pictures (b);
FIG. 8 is a photograph showing that the metal lead composite material with the addition amount of the MAX phase material of 5% in the embodiment 5 of the present application is formed into a sheet shape;
FIG. 9 is a diagram of a MAX phase material Ti according to example 6 of the present application 3 SiC 2 XRD patterns (a) and SEM pictures (b);
FIG. 10 is a diagram of a MAX phase material Ti according to example 7 of the present application 3 SnC 2 XRD patterns (a) and SEM pictures (b);
FIG. 11 is a diagram of a MAX phase material Ti according to example 8 of the present application 2 XRD spectrum (a) and SEM photograph (b) of SnC;
FIG. 12 shows the MAX phase material Ti in embodiment 10 of the application 3 AlC 2 (a) And MXene-MAX heterojunction material MXene-Ti 3 AlC 2 (b) SEM photographs of (2);
FIG. 13 is a metallic lead composite material incorporating MXene material and graphene material in example 16 of the present application.
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 adopted in the embodiment of the present application are purchased from beijing-tricyclopedia energy science and technology limited company, other raw materials and instruments, and the sources thereof are not particularly limited, and are purchased in the market or prepared according to conventional methods well known to those skilled in the art. The addition amount of the application refers to the mass percent of the additive in the metal lead or the metal lead alloy.
The MXene phase material is obtained by etching the A component in the MAX phase material, and the material with the characteristics of the accordion MXene material on the outside and the characteristics of the MAX phase material on the inside is obtained by controlling the etching degree, and is similar to the MXene-MAX heterojunction material with a 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 metal lead composite material and a preparation method thereof, and the method comprises the following steps:
1. heating and melting a metal lead ingot or a metal lead alloy into lead liquid;
2. adding an additive (at least one of an MXene material, an MXene-MAX heterojunction material and an MAX phase material) into the lead liquid according to a certain proportion, stirring and mixing the mixture to uniformly disperse the additive in the lead liquid to obtain lead slurry;
3. and cooling and solidifying the obtained lead slurry to obtain the metal lead composite material.
In some embodiments, in step 1, the metallic lead ingot is heated to 327 ℃ to 700 ℃;
in some embodiments, in step 2, the additive is added in an amount (by mass fraction) of from 0.01% to 95%; preferably between 0.01% and 80%; more preferably, between 0.01% and 50%; most preferably between 0.01% and 20%.
In some embodiments, metallic lead alloys include, but are not limited to, lead-tin alloys, lead-calcium alloys, lead-tin-calcium alloys, lead-antimony-tin alloys.
The metallic lead composite material of the present application means that metallic lead element is one of the main components of the material, or that the content of metallic lead element is at least 5wt.% or more, and does not include the case where lead element exists in the form of impurities or trace elements; preferably, the content of metallic lead element is greater than 20wt.%; more preferably, greater than 50wt.%, most preferably, greater than 80wt.%.
Example 2
The embodiment provides a specific metallic lead composite material and a preparation method thereof, wherein the additive is selected from an MXene material Ti with accordion shape 3 C 2 F x The XRD spectrum and SEM photograph are shown in FIG. 3, and the steps include:
1. heating 250g of the metal lead ingot to 400 ℃ to melt the metal lead ingot into lead liquid;
2. adding a predetermined mass of an MXene material (see Table 1) into the lead liquid, and stirring for 10-25 min at a stirring speed of 500rpm by using a metal stirrer to uniformly disperse the MXene material to obtain mixed lead slurry; FIGS. 4a and b show photographs of lead slurries with an addition of 5% and 30%, respectively, of an MXene material (runs No. 1 and 4 in Table 1), and it can be seen that the MXene material is dispersed in the lead liquid, indicating that the MXene material has a phase affinity with the molten lead liquid, which may result from the metallic nature of the MXene material itself containing a transition metal element; it is also possible that the surface from MXene has rich functional groups and reacts with metallic lead. The uniform dispersion of the MXene material in the lead liquid can be realized through the steps of stirring and the like; the uniform dispersion of MXene can effectively reduce the surface energy of lead liquid, and is beneficial to the addition of other materials such as graphene, carbon fiber, carbon nano tube, active carbon and porous carbon; uniformly mixing to obtain a metal lead composite material in which MXene and other materials are dispersed in metal lead;
3. pouring the mixed lead paste obtained in the step 2 into a preset mould for cooling and solidifying to obtain the metal lead composite material. The resulting metallic lead composite was tested for weight and bulk calculated density as shown in table 1 below:
TABLE 1 Density of metallic lead composite materials obtained with different MXene additions
In a specific embodiment, the shape of the mold can be changed in step 3 according to actual needs, so as to obtain metal lead composite materials with different shapes, such as lead ingots, lead plates, lead nets and the like. And 3, pouring the mixed lead slurry into an electrode grid die of the lead-acid battery, and obtaining a pole piece grid plate of the lead-acid battery after cooling and solidifying. The density of the metal lead composite material is obviously less than that of a lead ingot, and the total mass of the battery can be obviously reduced by adopting the metal lead composite material as the electrode grid of the lead-acid battery, so that the mass specific energy of the lead-acid battery can be further improved.
According to the manufacturing process of the lead-acid battery electrode grid, the actual addition amount of the MXene material, the MXene-MAX heterojunction material and the MAX phase material in the metal lead composite material can be further adjusted and optimized within the range of 0.01% -95%.
In contrast, fig. 5 gives a photograph of graphene added to molten lead, and it can be seen that graphene almost floats on the surface of molten lead, cannot be dispersed in the molten lead, and forms metallic shot on the pouring level of molten lead due to the high specific surface energy of molten lead.
Example 3
The embodiment provides another specific metallic lead composite material and a preparation method thereof, which is similar to the embodiment 2, but the difference is that the additive is MXene material Ti with two-dimensional morphology 3 C 2 F x The XRD spectrum and SEM photograph are shown in FIG. 6, and the two-dimensional MXene is obtained by stripping (such as ultrasonic) of an accordion-shaped MXene material, and has a remarkable two-dimensional lamellar structure (FIG. 6 b). The addition amount of the MXene material is between 0.1% and 30%; in a specific embodiment, the amount of MXene material added is 5%.
Example 4
This example provides another specific metallic lead composite material and method of making same, similar to example 2, except that the metallic lead ingot is replaced with a lead tin calcium alloy.
Example 5
The present example provides another specific metallic lead composite material and method of preparation, similar to that of example 2, except that the additive is a MAX phase material Ti 3 AlC 2 The XRD pattern and SEM photograph are shown in FIG. 7. Like the MXene material, the MAX phase material also has affinity to molten lead, and dispersion in the lead can be achieved by stirring. Fig. 8 shows a metallic lead composite sheet formed after pouring molten lead liquid with a MAX phase addition amount of 5% into a mold and horizontally spreading, cooling and solidifying, whereas molten lead liquid without additives is formed into a spherical shape (see fig. 5). The specific surface energy of molten lead can be obviously reduced after MAX phase material is added, so that the difficulty of processing and forming molten metal lead is greatly reduced. Table 2 shows the addition of different MAX phase materialsThe density of the obtained metal lead composite material is measured.
TABLE 2 Density of metallic lead composite materials obtained with different MAX phase Material addition
Example 6
The present example provides another specific metallic lead composite material and method of preparation, similar to that of example 2, except that the additive is a MAX phase material Ti 3 SiC 2 The XRD pattern and SEM photograph are shown in FIG. 9. The addition amount of MAX phase material is 0.1-30%; in a specific embodiment, the MAX phase material is added in an amount of 5%.
Example 7
The present example provides another specific metallic lead composite material and method of preparation, similar to that of example 2, except that the additive is a MAX phase material Ti 3 SnC 2 The XRD pattern and SEM photograph are shown in FIG. 10. The addition amount of MAX phase material is 0.1-30%; in a specific embodiment, the MAX phase material is added in an amount of 5%.
Example 8
The present example provides another specific metallic lead composite material and method of preparation, similar to that of example 2, except that the additive is a MAX phase material Ti 2 SnC, XRD spectrum and SEM photograph are shown in figure 11, and the addition amount of MAX phase material is 0.1-30%; in a specific embodiment, the MAX phase material is added in an amount of 0.5%.
Example 9
The embodiment provides another specific metal lead composite material and a preparation method thereof, wherein a metal lead alloy is selected to be compounded with a MAX phase material, specifically, the metal lead alloy is selected to be lead tin calcium alloy, and the MAX phase material is selected to be additive Ti 3 SnC 2 The implementation steps comprise:
1. heating 250g of lead-tin-calcium alloy to 400 ℃ to melt the lead-tin-calcium alloy into lead liquid;
2. will be of a predetermined mass of Ti 3 SnC 2 Adding the powder into the lead liquid, and stirring for 10-25 min at a stirring speed of 500rpm by using a metal stirrer so as to uniformly disperse the MAX phase material and obtain mixed lead slurry;
3. pouring the mixed lead paste obtained in the step 2 into a preset mould for cooling and solidifying to obtain the metal lead composite material.
Ti 3 SnC 2 The amount of the powder to be added is preferably adjusted to be in the range of 0.1% to 50%, in this embodiment, ti 3 SnC 2 The amount of the powder added was 1% (2.5 g).
The lead-tin-calcium alloy in this embodiment may also be replaced with other types of metallic lead alloys including, but not limited to, lead-tin alloys, lead-calcium alloys, lead-antimony-tin alloys.
Example 10
The present example provides another specific metallic lead composite material and method of making same, similar to example 2, except that the MXene material is replaced with a MXene-MAX heterojunction material MXene-Ti 3 AlC 2 . As the MXene-MAX phase material belongs to the intermediate state of the accordion MXene material and the MAX phase material, the material also has the affinity with molten lead liquid.
FIG. 12 shows 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. The rough surface is derived from the open accordion shape generated by partial etching, molten lead can infiltrate into open gaps, and after cooling and solidification, the molten lead is cooled and solidified in MXene-Ti 3 AlC 2 The surface forms a micro mortise and tenon structure, and the MXene-Ti is improved 3 AlC 2 And the interfacial bonding force with the metallic lead can further improve the mechanical property.
In a specific embodiment MXene-Ti 3 AlC 2 The addition amount of (2) is 0.1 to 50%; in a specific embodiment, MXene-Ti 3 AlC 2 The addition amount of (2) is 5%。
In another specific embodiment, MXene-Ti 3 AlC 2 The addition amount of (2) was 10%.
In another specific embodiment, MXene-Ti 3 AlC 2 The addition amount of (2) was 0.1%.
In another specific embodiment, MXene-Ti 3 AlC 2 The addition amount of (2) was 40%.
Example 11
The present example provides another specific metallic lead composite material and method of making same, similar to example 10, except that the MXene-MAX heterojunction material is replaced with MXene-Ti 3 SiC 2 。
In a specific embodiment MXene-Ti 3 SiC 2 The addition amount of (2) is 0.1 to 50%; in a specific embodiment, MXene-Ti 3 SiC 2 The addition amount of (2) was 5%.
Example 12
The present example provides another specific metallic lead composite material and method of making same, similar to example 10, except that the MXene-MAX heterojunction material is replaced with MXene-Ti 3 SnC 2 。
In a specific embodiment MXene-Ti 3 SnC 2 The addition amount of (2) is 0.1 to 50%; in a specific embodiment, MXene-Ti 3 SnC 2 The addition amount of (2) was 5%.
The metal lead composite material provided by the embodiment can be injected into an electrode grid through molten mixed lead slurry to be cooled, solidified and molded to obtain the electrode grid; or the mixed lead slurry is cooled and solidified into a metal ingot, and then the electrode grid is manufactured through different forming processes.
Example 13
The embodiment provides an electrode grid of a lead-acid battery, wherein the electrode grid is made of the metal lead composite material; the preparation method comprises the following steps: the metal lead composite material is heated and melted into composite lead slurry, and then poured into an electrode grid die to be cooled and solidified, thus obtaining the electrode grid.
In a specific embodiment, the metal composite material obtained in example 2 is used, wherein the additive is selected from the group consisting of an MXene material Ti having an accordion morphology 3 C 2 F x The addition amounts were 5% and 10%.
In another embodiment, the metal composite material obtained in example 6 is used, wherein the additive is selected from the MAX phase material Ti 3 AlC 2 The addition amounts were 5% and 10%.
In another embodiment, the metal composite material obtained in example 10 is used, wherein the additive is selected from the group consisting of MXene-MAX heterojunction material MXene-Ti 3 AlC 2 The addition amounts were 5% and 10%.
The metal lead composite material is heated and melted into composite lead slurry, and then poured into a designed mould to obtain the test grid plate with the length, the width and the thickness of 5cm, 2cm and 0.3 cm. The additive-free metallic lead obtained by the same method is used as a comparative lead plate.
The metal lead composite material of the application is used as the corrosion resistance of the electrode grid, and is tested by adopting a constant current corrosion weightlessness method, and the testing method comprises the following steps: record the initial mass of the test grid (m 1 ) Then the test grid plate is put into an electrolytic tank filled with sulfuric acid solution (the mass concentration is 40%) to be used as an anode, a cadmium electrode is used as a cathode, and the current density is 10mA/cm in the room temperature environment 2 Constant-current charging is carried out for 400 hours, after charging is completed, the test grid plate is cleaned to remove surface corrosive substances, and then is dried and weighed, so that the corrosion quality m is obtained 2 The weight loss Δm=m of the test grid was calculated 1 -m 2 And the weight loss rate delta= delta m/m 1 . The tensile strength of the metal lead composite material serving as the mechanical property of the electrode grid is tested according to the test method specified in GB/T228.1 2010. The results are shown in Table 3 below:
TABLE 3 Corrosion resistance test and mechanical Property test of metallic lead composite Material of the application
As can be seen from the test results of Table 3, the metallic lead composite material containing the additives MXene material, MAX phase material and MXene-heterojunction material of the present application has significantly improved corrosion resistance compared with the comparative lead plate, which is related to the excellent corrosion resistance of the additives of the present application, on the one hand, and the uniform dispersion of the additives of the present application in the metallic lead composite material due to the affinity of the additives of the present application with the metallic lead liquid, on the other hand. From the comparison of mechanical properties, the performance of the metal lead composite material added with the additive is obviously improved, and the metal lead composite material is related to the uniform dispersion of the added MXene material or MAX phase material in the metal lead composite material and the affinity of a metal lead interface, so that the problems of softening and breaking of an electrode grid of a lead-acid battery are solved, and particularly, the performance of the metal lead composite material added with the MXene material and the MXene-MAX phase material is better, and the two-dimensional structure of the MXene material can be used for dispersing in the metal lead composite material to form a network structure, so that the mechanical property is more effectively improved; the surface of the MXene-MAX heterojunction material is provided with an opening accordion shape of the MXene material, molten lead liquid can infiltrate into an opening gap, a micro tenon-and-mortise structure is formed on the surface after cooling and solidification, the interfacial binding force of the MXene-MAX heterojunction material and metal lead is improved, and the mechanical property can be improved. From the comprehensive performance, the MXene-MAX heterojunction material has better corrosion resistance and mechanical property, and is more preferable as an additive.
PbO, a strong oxidation product, is present in lead acid battery positive grid coated positive electrode materials 2 And higher requirements are put on oxidation resistance and corrosion resistance of the positive grid. The metallic lead composite material of the present application is used for a positive grid, preferably the additive contains a MAX phase material or a MXene-MAX heterojunction material, more preferably a MAX phase material or a MXene-MAX heterojunction material with a component of Sn and Si, which has better oxidation resistance, corrosion resistance and stability, still more preferably the additive contains a MAX phase material or a MXene-MAX phase material with a component of Sn, because such a Sn-containing material will not form after being oxidized in a small amountSnO dissolved in sulfuric acid 2 Not only can prevent the grid from being further oxidized, but also can prevent the grid from being oxidized due to SnO 2 The positive grid has conductivity, ensures the high conductivity of the whole positive grid, and effectively solves the problems that the positive grid of the prior lead-acid battery is easy to be corroded and oxidized to cause the falling and failure of active substances.
Example 14
The embodiment provides an electrode grid of a lead-acid battery and a preparation method thereof, wherein an MXene material and a MAX phase material are added simultaneously, and the method comprises the following steps:
1. heating and melting a metal lead ingot or a metal lead alloy into lead liquid;
2. adding an additive MXene material and an MAX phase material into the lead liquid according to a certain proportion, stirring and mixing the materials to uniformly disperse the additive in the lead liquid to obtain lead slurry;
3. and injecting the lead slurry into an electrode grid die, solidifying, cooling and forming to obtain the electrode grid of the lead-acid battery.
Optionally, the mass ratio of the MXene material to the MAX phase material can be adjusted within the range of (0.1-10): 1, two composite additives are selected, and the electrode grid with mechanical property, corrosion resistance and oxidation resistance is obtained by utilizing the two-dimensional structural characteristic of the MXene material and the more excellent oxidation resistance and corrosion resistance of the MAX phase material and through limited experimental screening.
In a specific implementation of this embodiment, the metallic lead alloy is Pb-Sn-Ca alloy, and the MXene material is Ti 3 C 2 F x The MAX phase material is Ti as additive 3 SnC 2 The implementation steps comprise:
1. heating 250g of lead-tin-calcium alloy to 400 ℃ to melt the lead-tin-calcium alloy into lead liquid;
2. will be of a predetermined mass of Ti 3 C 2 F x 、Ti 3 SnC 2 Adding the powder into the lead liquid, and stirring for 10-25 min at a stirring speed of 500rpm by using a metal stirrer so as to uniformly disperse the MXene material and the MAX phase material and obtain mixed lead slurry;
3. pouring the mixed lead paste obtained in the step 2 into a preset mould for cooling and solidifying to obtain the electrode grid.
In a more specific embodiment Ti 3 C 2 F x With Ti 3 SnC 2 The mass ratio of the powder is (0.5-5): 1, in this example 1:1.
Example 15
Because the MXene material, the MXene-MAX heterojunction material and the MAX phase material have compatibility with molten lead liquid, that is, the specific surface energy of the molten lead liquid can be effectively reduced by adding the materials into the molten lead liquid, and based on the characteristic, other materials such as carbon materials, metal oxides and the like can be mixed into the molten lead liquid after the specific surface area of the molten lead liquid is reduced, so that the density, mechanical property, oxidation resistance, corrosion resistance and the like of the metal lead composite material can be further regulated and controlled, and the novel metal lead composite material is obtained and used for developing novel light lead-acid battery grids.
In this embodiment, there is provided an electrode grid of a lead-acid battery and a method for manufacturing the same, wherein the steps include:
1. heating and melting a metal lead ingot or a metal lead alloy into lead liquid;
2. adding at least one of an additive MXene material, an MXene-MAX heterojunction material and an MAX phase material (first additive) into the lead liquid according to a certain proportion, stirring and mixing to uniformly disperse the additive in the lead liquid to obtain lead slurry;
3. adding a second additive into the lead paste in the step 2, and stirring and dispersing; wherein the second additive may be one or more of graphite, expanded graphite, graphene, carbon fiber, carbon nanotube, activated carbon, porous carbon, carbon aerogel.
4. And (3) injecting the lead slurry obtained in the step (3) into an electrode grid die, solidifying, cooling and forming to obtain the electrode grid of the lead-acid battery.
In one embodiment, the addition amount of the (first additive) accounts for 0.1-50% of the mass of the metal lead or the metal lead alloy; preferably, between 1% and 20%; the addition amount of the second additive accounts for 0.1-50% of the mass of the metal lead or the metal lead alloy; preferably between 1% and 20%.
In one embodiment, the mass ratio of the first additive to the second additive is between (0.1 and 10): 1.
example 16
The embodiment provides a metallic lead composite material and a preparation method thereof, and the specific implementation steps comprise:
1. heating 250g of metal lead ingot to 400 ℃ to melt the lead-tin-calcium alloy into lead liquid;
2. will be of a predetermined mass of Ti 3 C 2 F x Adding the powder into the lead liquid, and stirring for 10-25 min at a stirring speed of 500rpm by using a metal stirrer so as to uniformly disperse the MXene material and obtain mixed lead slurry;
3. adding graphene with preset mass into the mixed lead slurry in the step 2, and stirring and dispersing;
4. pouring the mixed lead slurry obtained in the step 3 into a preset mold for cooling and curing to obtain the metal lead composite material.
In a more specific embodiment, ti 3 C 2 F x The amount of powder added is 5% of the mass of the metal lead alloy, the amount of graphene added is 5%, fig. 13 shows a photograph of the obtained metal lead composite material containing MXene material and graphene material, and it can be seen that graphene is uniformly mixed into the metal lead, unlike fig. 5 where graphene is difficult to add into molten lead, which is related to the significant decrease of specific surface energy of molten lead due to the addition of MXene material.
Similarly, the graphene in the present embodiment may also be replaced with other types of carbon materials, including but not limited to one or more of graphite, expanded graphite, graphene, carbon fiber, carbon nanotube, activated carbon, porous carbon, carbon aerogel.
It should be noted that, since the MXene material is a two-dimensional material, the chemical formula is represented 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; t (T) x Represents a functional group of the polymer, comprising-F, -Cl, br, I, -O, -S, -OH, -NH 4 One or more of the following; n is more than or equal to 1 and less than or equal to 4. Similarly, MAX phase materials are also a type of ceramic materials, represented by the chemical formula 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; n is more than or equal to 1 and less than or equal to 4. Under the teaching of the application, other types of MXene materials, MXene-MAX heterojunction materials and MAX phase materials are selected for being compounded with metal lead to obtain the metal lead composite material, or the metal lead composite material is used for an electrode grid of a lead-acid battery, and the metal lead composite material belongs to the technical concept of the application.
The MXene material, the MXene-MAX heterojunction material and the MAX phase material existing in the electrode grid can be characterized by XRD tests.
The electrode grid of the application can be used for the positive electrode and the negative electrode of a lead-acid battery. The lead-acid battery containing the electrode grid is particularly suitable for electric vehicles, including electric bicycles, electric automobiles and the like, and can also be used as a starting and stopping battery of a vehicle.
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 (17)

1. A metallic lead composite material, comprising: metallic lead or metallic lead alloy;
and, an additive; the additive comprises: at least one of an MXene material and an MXene-MAX heterojunction material;
the preparation method of the metal lead composite material comprises the following steps: the additive is mixed with molten metallic lead or metallic lead alloy.
2. The metallic lead composite material of claim 1, 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;
and/or the MXene-MAX heterojunction material is obtained by partially etching the A component by MAX phase material;
and/or the metal lead alloy comprises at least one of lead-tin alloy, lead-calcium alloy, lead-tin-calcium alloy and lead-antimony-tin alloy;
and/or the additive also comprises MAX phase material.
3. The metallic lead composite of claim 2, wherein M in the MXene material chemical formula is selected from at least one of Ti, V, mo, nb, ta, W, cr.
4. The metallic lead composite of claim 2, wherein the MXene-MAX heterojunction material is derived from a MAX phase material partially etching a composition, the MAX phase material M being selected from at least one of Ti, V, mo, nb, ta, W, cr, and/or a being selected from Sn or Si elements.
5. The metallic lead composite material as recited in any one of claims 1 to 4, wherein the additive is present in an amount between 0.01% and 95% by mass;
and/or, the content of metallic lead element in the metallic lead composite material is at least more than 5wt.%;
and/or the additive further comprises a carbon material.
6. The metallic lead composite material as recited in claim 5, wherein the metallic lead composite material comprises the additive in an amount of between 0.01% and 80% by mass; and/or the mass content of metallic lead element is greater than 20wt.%.
7. The metallic lead composite material as recited in claim 5, wherein the metallic lead composite material comprises the additive in an amount of between 0.01% and 50% by mass; and/or the mass content of metallic lead element is greater than 50wt.%.
8. The metallic lead composite material as recited in claim 5, wherein the metallic lead composite material comprises the additive in an amount of between 0.01% and 20% by mass; and/or the mass content of metallic lead element is greater than 80wt.%.
9. The metallic lead composite of claim 5, wherein the carbon material is selected from one or more of graphite, expanded graphite, graphene, carbon fibers, carbon nanotubes, activated carbon, porous carbon, carbon aerogel.
10. Use of the metallic lead composite material of any one of claims 1 to 9 for an electrode grid of a lead acid battery.
11. A method of producing a metallic lead composite material as claimed in any one of claims 1 to 9, characterized in that the steps include: heating and melting metallic lead into lead liquid, adding an additive into the lead liquid, and stirring to obtain mixed lead slurry; and cooling and solidifying the mixed lead slurry to obtain the metal lead composite material.
12. An electrode grid obtained by molding the metal lead composite material according to any one of claims 1 to 9.
13. The method for preparing the electrode grid of claim 12, comprising the steps of:
heating and melting metallic lead into lead liquid, adding an additive into the lead liquid, and stirring to obtain mixed lead slurry;
injecting the mixed lead slurry into an electrode grid die, and cooling and solidifying to obtain the electrode grid;
or coating the mixed lead paste on grids made of other materials to obtain the electrode grid;
wherein the additive comprises: at least one of MXene material and MXene-MAX heterojunction material.
14. A lead acid battery electrode comprising: positive and negative electrodes, wherein the lead-acid battery electrode comprises the electrode grid of claim 12;
or, the lead-acid battery electrode contains the electrode grid obtained by the preparation method of claim 13.
15. A lead acid battery comprising the electrode grid of claim 12;
or, the lead-acid battery comprises the electrode grid obtained by the preparation method of claim 13.
16. An electric vehicle comprising the lead acid battery of claim 15.
17. A vehicle comprising the lead acid battery of claim 15.
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