CN113948701B - Active carbon composite material and application thereof in lead-carbon battery - Google Patents

Active carbon composite material and application thereof in lead-carbon battery Download PDF

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CN113948701B
CN113948701B CN202010693361.4A CN202010693361A CN113948701B CN 113948701 B CN113948701 B CN 113948701B CN 202010693361 A CN202010693361 A CN 202010693361A CN 113948701 B CN113948701 B CN 113948701B
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lead
composite material
hydrogen evolution
battery
carbon
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CN113948701A (en
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席耀宁
李先锋
阎景旺
张华民
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment
    • 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
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a lead-carbon battery, in particular to an active carbon composite material which is prepared by the following method: 1) Preparing solution A: blending the soluble salt of the high hydrogen evolution overpotential element and the high polymer water solution into the solution A in water; 2) Preparing slurry B: dropwise adding the solution A into the porous activated carbon material while stirring to form a slurry B; 3) Placing the slurry B in a stirring state at the temperature of-4-4 ℃, and dropwise adding a strong reducing agent solution into the slurry B; 4) And drying to obtain the monodisperse atom cluster-porous activated carbon composite material. The invention solves the serious hydrogen evolution problem of the lead-carbon battery after adding the carbon material by utilizing the hydrogen evolution inhibitor.

Description

Active carbon composite material and application thereof in lead-carbon battery
Technical Field
The invention relates to the field of lead-carbon batteries, in particular to the field of energy storage batteries and power-on and power-off batteries.
Background
At present, although lead-acid batteries still occupy a major share of the energy storage battery market, the position of lead-acid batteries in the energy storage market has been moved along with the development and application of various novel energy storage batteries. The main reason for the progressive loss of market for lead-acid batteries is that other types of energy storage batteries often have higher energy densities or longer service lives, and lead-carbon batteries have been developed to address the opportunities and challenges presented by the market.
The lead-carbon battery is a novel battery which is the easiest to replace lead-acid batteries at present, and is characterized by long cycle life, low cost and relatively perfect industrial production process. The lead-carbon battery is characterized in that a certain amount of active carbon and conductive carbon materials are doped into a negative plate of the lead-acid battery, so that the sulfation problem in the battery operation process is solved to the greatest extent, and the service life of the battery is effectively prolonged.
However, the common active carbon is introduced into the negative electrode to greatly increase the hydrogen evolution current of the negative electrode, so that the water consumption is particularly serious in the use process of the battery, and finally the battery is invalid, and therefore, the problem of hydrogen evolution of the negative electrode of the lead-acid battery can be solved, and the lead-acid battery can comprehensively replace the lead-acid battery. The elements such as lead, indium and the like have higher hydrogen evolution potential and reduction potential, so that the metal ions are uniformly distributed on the surface of the active carbon to occupy the hydrogen evolution active site, thereby effectively inhibiting the hydrogen evolution of the active carbon and further greatly prolonging the service life of the lead carbon battery.
The common adding mode of inhibiting the hydrogen evolution agent is to introduce the high hydrogen evolution overpotential element into the surface and the holes of the carbon material in a dissolving-adsorbing-recrystallizing mode, and the mode can play a role of inhibiting the hydrogen evolution agent to a certain extent, but the effect of inhibiting the hydrogen evolution agent is difficult to play to the maximum extent due to the randomness of the crystallization process of the hydrogen evolution agent.
In order to solve the problems, the atomic cluster-level hydrogen evolution inhibitor-activated carbon composite material provided by the invention can effectively play a role of inhibiting the hydrogen evolution inhibitor, reduce the purchase cost of the additive and greatly prolong the service life of the existing lead-carbon battery.
Disclosure of Invention
The invention solves the serious hydrogen evolution problem of the lead-carbon battery after adding the carbon material by utilizing the hydrogen evolution inhibitor.
The utilization rate of the hydrogen evolution inhibitor is improved by uniformly dispersing the high hydrogen evolution overpotential element atomic clusters on the surface of the carbon material.
The invention develops a method for preparing atomic clusters on the surface of a carbon material of a lead-carbon battery. The preparation method comprises the following steps:
1) Preparing solution A:
the method comprises the steps of blending a soluble salt of a high hydrogen evolution overpotential element and a high polymer aqueous solution into a solution A in water, wherein the concentration of the soluble salt of the high hydrogen evolution overpotential element in the solution A is 1-10mg/ml, preferably 2-5mg/ml, the mass concentration of the high polymer aqueous solution is 20-60wt%, and the mass ratio of the high polymer to the high hydrogen evolution overpotential element in the solution A is 0.1-20:1, a step of; preferably in a mass ratio of 8-15:1.
2) Preparing slurry B:
drop A into porous active carbon material while stirring into B slurry state, wherein the mole of high hydrogen evolution overpotential elementThe ratio of the number to the surface area of the carbon material was 1mmol:2000-30000m 2 The method comprises the steps of carrying out a first treatment on the surface of the (the surface area of the carbon material is the sum of the inner surface of the pore canal and the outer surface area of the material, i.e. the specific surface area multiplied by the mass of the activated carbon), preferably 1mmol:15000-25000m 2。
3) Placing the slurry B in a stirring state at the temperature of-4-4 ℃, dropwise adding a strong reducing agent solution with the concentration of 1-10g/L into the slurry B, continuously stirring for 0.5-24h after dropwise adding, wherein the strong reducing agent comprises the following components in a molar ratio of high hydrogen evolution overpotential elements of=1-30: 1, preferably 10-30:1.
4) Drying for 1-24 hours at 60-120 ℃ to obtain the monodisperse atom cluster-porous active carbon composite material, wherein the particle size of the monodisperse atom cluster is 0.1-5nm.
The high molecular polymer (polymers) is sodium polymethacrylate (PMAA-Na) and/or polyethylene glycol dimethacrylate (PEGDMA-Na);
the high hydrogen evolution overpotential element comprises one or more of Indium (Indium), lead (lead), zinc (zinc), gallium (gallium), cerium (cerium) and bismuth (bismputh);
the strong reducing agent solution (strong reducing agent or reductant) is one or more than two of 1-10g/L of aqueous solution, sodium borohydride (Sodium borohydride), 1-10g/L of aqueous solution, hydrogen peroxide (hydrogen peroxide), 1-10g/L of aqueous solution and hydrazine hydrate (hydrazine hydrate);
the soluble salt of the high hydrogen evolution overpotential element is one of soluble nitrate, sulfate, phosphate and chloride.
The size of the atomic clusters of the high hydrogen evolution overpotential element in the prepared monodisperse atomic cluster-active carbon composite material is 0.1-10nm.
The composite material is applied to the lead-carbon battery electrode.
The lead-carbon battery electrode comprises the following materials: 500-800 parts of lead powder, 1-20 parts of the porous active carbon composite material prepared in the step 1, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
The preparation process of the lead-carbon battery electrode comprises the following steps: (1) Premixing 500-800 parts of lead powder, 1-20 parts of the porous activated carbon composite material according to any one of claims 1-5, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m by a high-speed mixer, adding 50-100 parts of deionized water into the premixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) Scraping lead plaster on a metal lead grid with the size of 50-1000mm, the width of 20-80mm and the thickness of 0.5-4mm, and drying and solidifying to obtain a lead-carbon battery cathode; the curing temperature is 30-50 ℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 ℃ and the drying time is 10-30 hours.
The invention has the beneficial effects that:
the invention utilizes the mode that the high molecular polymer ligand coats the high hydrogen evolution overpotential element ions to form a complex, thereby realizing the high dispersion of the high hydrogen evolution overpotential element in the form of atomic clusters. In the preparation process, the complex solution is dropwise added into the porous carbon material, the complex is instantaneously adsorbed into the porous carbon material in a large amount, the complex solution is fully filled into pores of the porous carbon material, the complex solution is continuously dropwise added along with the saturation of the complex solution in the porous carbon, a slurry state is gradually formed under the stirring condition, the ratio between the mole number of the high hydrogen evolution overpotential element and the surface area of the carbon material is controlled, and the excessive strong reducing agent is dropwise added under the low-temperature stirring condition, so that the porous active carbon composite material containing the monodisperse atomic clusters is obtained.
Compared with the existing preparation method, the atomic cluster-level hydrogen evolution inhibiting metal contained in the unit area of the carbon material prepared by the preparation method has higher content concentration, more uniform dispersion and smaller size, and the diameter of the generated nano particles is about 1 nm. The binding force with the carbon material is higher, the utilization rate of inhibiting the hydrogen evolution agent can be greatly improved when the catalyst is applied to a lead-carbon battery, the poisoning cost is reduced, the water consumption in the use process of the battery is reduced, and the service life of the battery is prolonged.
Drawings
FIG. 1 is a morphology diagram of a monodisperse atom cluster-activated carbon composite;
FIG. 2 shows LSV test results of lead-carbon batteries prepared in different examples or comparative examples;
Detailed Description
The present invention is described in detail below with reference to examples.
Unless otherwise specified, the starting materials in the examples were purchased commercially and used without treatment; the instrument and equipment are recommended to use parameters by manufacturers.
In the examples, the cycle life of the lead-carbon battery was tested using a blue charge-discharge tester and a new-wire charge-discharge tester.
In an embodiment, a transmission electron microscope is used to observe the morphology of the atomic clusters.
Example 1
Step 1, preparing a monodisperse atom cluster-activated carbon composite material by adopting the following method:
1) Preparing solution A:
300mg of indium nitrate are dissolved together with 5ml of 40wt% sodium polymethacrylate (PMAA-Na) solution in 100ml of water;
2) Preparing slurry B:
dropwise adding the solution A into 10g of active carbon material while stirring to form a slurry B; the specific surface area of the activated carbon is 1800m 2 /g; the activated carbon used was tested and calculated to have a surface area of approximately 18000m 2 ；
3) The B slurry was stirred in an ice-water bath at 0℃to prepare 0.5g of sodium borohydride (NaBH) 4 ) Dissolving in 100ml of water, dripping into the slurry B for 10min, and continuously stirring for 2h after dripping;
4) Drying for 12 hours at 80 ℃ to obtain the monodisperse atom cluster-activated carbon composite material.
The morphology of the prepared monodisperse atom cluster-activated carbon composite material is shown in figure 1, and the size of the atom cluster is about 1 nm.
And 2, preparing a lead-carbon battery cathode by adopting the following steps: (1) Premixing 600g of lead powder, 9g of the carbon material prepared in the step 1, 8.4g of barium sulfate and 0.3g of polypropylene short fiber with the length of 5mm and the diameter of 0.5-1.5 mu m by a high-speed stirrer, adding 84g of deionized water into the premixed powder while stirring, and continuously stirring for 10min to obtain lead plaster; (2) And (3) scraping the lead plaster on a metal lead grid, wherein the size of the grid is 70mm long and 50mm wide and 2mm thick, and solidifying and drying to obtain the negative electrode of the lead-carbon battery. Curing temperature is 40 ℃, humidity is 80 percent, and curing time is 20 hours; the drying temperature is 80 ℃ and the drying time is 24 hours; (3) The lead-acid battery anode is prepared by adopting the same process, two internal mixing type lead-acid battery electrodes with modified active carbon are connected in parallel to serve as a negative electrode, and the internal mixing type lead-acid battery is assembled by connecting the two internal mixing type lead-acid battery electrodes with modified active carbon in series with the three parallel lead-acid battery anodes. Wherein the positive electrode active material of the lead-acid battery is 20.0g of lead oxide, the total mass of the negative electrode active material is 14.3g, the positive and negative electrode plate grids adopt conventional lead grids, and the size is 70mm long, 50mm wide and 2mm thick; (4) And sequentially arranging the three positive plates and the two negative plates alternately at intervals in parallel, and arranging PE (polyethylene) diaphragms of the commercial lead-acid battery between the positive plates and the negative plates. Placing the anode and the cathode in a tightly assembled battery box, wherein the length of the battery box is 76mm, the width of the battery box is 40mm, the height of the battery box is 100mm, and 83g of sulfuric acid electrolyte with the density of 1.275g/ml is injected into the battery box; (5) subjecting the battery to a life test under the following conditions: and (3) adopting 4.2A constant current discharge for 59 seconds, 18A discharge for 1 second, adopting 6.3A current for 2.3V voltage constant current constant voltage charge for 60 seconds, cycling the charge and discharge conditions 3600 times, then standing for 40 hours, restarting cycling after 40 hours, and reducing the battery voltage to below 1.2V as the end condition of life test. The assembled internal mix battery. The initial voltage of the battery in the full-charge state is 2.19V, and the internal mixed battery can run for 18000 circles under the condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 2.5 times of that of the conventional lead-acid battery.
Example 2
Lead carbon battery according to the requirements of example 1, sodium polymethacrylate (PMAA-Na) was replaced by polyethylene glycol dimethacrylate added with the same volume and concentration without changing other conditions. The prepared lead-carbon battery negative electrode active material 0.21g is taken as a working electrode, the positive electrode active material 0.36g is taken as a counter electrode, a commercial mercury-mercurous sulfate reference electrode is taken for carrying out a three-electrode system LSV test, the test range is (-1) V to (-1.6) V, and the test result is shown in figure 2. The morphology of the prepared monodisperse atom cluster-activated carbon composite material can be seen that the size of the atom cluster is about 1 nm.
Example 3
According to the requirements of example 1, the addition amount of indium nitrate was changed to 600mg without changing other conditions. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 2 times of that of the conventional lead-acid battery. The morphology of the prepared monodisperse atom cluster-activated carbon composite material can be seen that the size of the atom cluster is about 3 nm.
Example 4
The amount of PMAA-Na added was changed to 10ml according to the requirements of example 1 without changing other conditions. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 2 times of that of the conventional lead-acid battery. The morphology of the prepared monodisperse atom cluster-activated carbon composite material can be seen that the size of the atom cluster is about 0.8 nm.
Example 5
According to the requirements of example 1, naBH was applied without changing other conditions 4 The addition amount of (2) was changed to 1g. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 2 times of that of the conventional lead-acid battery. The morphology of the prepared monodisperse atom cluster-activated carbon composite material can be seen that the size of the atom cluster is about 0.8 nm.
Example 6
The amount of PMAA-Na added was changed to 0.1ml according to the requirements of example 1 without changing other conditions. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 2 times of that of the conventional lead-acid battery. The morphology of the prepared monodisperse atom cluster-activated carbon composite material can be seen that the size of the atom cluster is about 4 nm.
Example 7
According to the requirements of example 1, a low specific surface area activated carbon material was used, with a specific surface area of about 200m, without changing other conditions 2 And/g, and preparing a corresponding lead-carbon battery. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery only reaches 2 times of that of the conventional lead-acid battery. The size of the prepared monodisperse atom cluster is about 1 nm.
Example 8
According to the requirements of example 1, a specific surface of 3000m was used without changing other conditions 2 And (3) preparing the active carbon material of/g, and preparing the corresponding lead-carbon battery under the same quality. The internal mix battery can run 14400 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery only reaches 2 times of that of the conventional lead-acid battery. The size of the prepared monodisperse atom cluster is about 1 nm.
Example 9
Lead carbon battery according to the requirements of example 1, indium nitrate was replaced with zinc nitrate in the same number of moles without changing other conditions. LSV testing was performed as in example 2, with the test results shown in fig. 2. The size of the prepared monodisperse atom cluster is about 1 nm.
Comparative example 1
Lead-acid battery according to the requirements of example 1, without changing other conditions, without carrying out the material preparation of step 1, and without adding any carbon material in step 2, a lead-acid battery is prepared. The battery can run for 7200 cycles.
Comparative example 2
The lead-carbon battery cathode adopts 9g of the specific surface area of 1300m 2 Commercial activated carbon per gram. The assembled internal mix battery can run 10800 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 1.5 times of that of the conventional lead-acid battery.
Comparative example 3
Lead-carbon battery: according to the requirements of example 1, the metal element powder and the activated carbon powder of equal mass are directly added by adopting a mechanical mixing mode without changing other conditions. The internal mix battery can run 10800 cycles under this condition. Compared with the test result of the common lead-acid battery with the same lead element content under the same test condition (7200 circles), the service life of the internal mixed lead-acid carbon battery can reach 1.5 times of that of the conventional lead-acid battery.
Comparative example 4
Lead-carbon battery according to the requirement of example 1, the activated carbon is replaced by the activated carbon with the same mass and the specific surface area of 150m 2 And/g. LSV testing was performed as in example 2, with the test results shown in fig. 2.
Comparative example 5
Lead carbon battery the product was reduced by replacing sodium borohydride with the same number of moles of ascorbic acid (weak reducing agent) as required in example 1, without changing other conditions. LSV testing was performed as in example 2, with the test results shown in fig. 2.
Comparative example 6
Lead carbon battery according to the requirements of example 1, other conditions were not changed, and sodium polymethacrylate (PMAA-Na) was not added. LSV testing was performed as in example 2, with the test results shown in fig. 2. The size of the prepared monodisperse atom cluster is unevenly dispersed in the range of 50-500 nm.
Comparative example 7
Lead carbon battery according to the requirements of example 1, the experimental method of "4) in step 1) was carried out without changing other conditions: the solution A was slowly added dropwise to the solution B (the solution B was kept in a stirred state) to obtain an AB mixture. And (3) placing the AB mixed solution into an ice water bath at the temperature of 0 ℃ to keep stirring for 30min, slowly dropwise adding the C solution into the AB mixed solution, and stirring the ice water bath for 2 h. The experimental method is changed to' 4): the solution A was slowly added dropwise to the solution B (the solution B was kept in a stirred state) to obtain an AB mixture. The AB mixed solution is placed in a water bath at 80 ℃ and kept stirring for 30min, and the C solution is slowly added into the AB mixed solution in a dropwise manner and stirred for 2h in the water bath at 80 ℃. The particle size of the obtained atomic cluster is 200-500nm, and the prepared lead-carbon battery can only run 2506 circles and cannot complete the first large cycle of life test.
Comparative example 8
The amount of PMAA-Na added was changed to 0.01ml according to the requirements of example 1 without changing other conditions. The internal mix battery can run 3600 turns under this condition. Compared with the test result (7200 circles) of the common lead-acid battery with the same lead element content under the same test condition, the service life of the internal mixed lead-acid carbon battery only reaches 50% of that of the conventional lead-acid battery. The size of the prepared monodisperse atom cluster is unevenly dispersed in the range of 50-500 nm.
Comparative example 9
The amount of PMAA-Na added was changed to 30ml according to the requirements of example 1 without changing other conditions. The internal mix battery can run 3600 turns under this condition. Compared with the test result (7200 circles) of the common lead-acid battery with the same lead element content under the same test condition, the service life of the internal mixed lead-acid carbon battery only reaches 50% of that of the conventional lead-acid battery. The size of the prepared monodisperse atom cluster is about 1 nm.
As can be seen from the LSV test results of fig. 2, the highest hydrogen evolution current densities of the different examples and comparative examples: the composite carbon material obtained by the preparation method is 88mA/g in example 1, 91mA/g in example 2, 149mA/g in example 9, 410mA/g in comparative example 4, 528mA/g in comparative example 5 and 554mA/g in comparative example 6, and compared with the condition of comparative examples, the composite carbon material obtained by the preparation method is applied to a lead-carbon battery, and the high-hydrogen-evolution overpotential element is highly dispersed in atomic clusters by coating the high-molecular polymer ligand to form a complex. In the preparation process, a complex precursor aqueous solution is dropwise added into a porous carbon material, a large amount of complex is instantaneously adsorbed into the porous carbon material, the complex solution is fully filled into pores of the porous carbon material, the complex solution is continuously dropwise added along with the saturation of the complex solution in the porous carbon, a slurry state is gradually formed under the stirring condition, the proportion between the mole number of high hydrogen evolution overpotential elements and the surface area of the carbon material is controlled, and an excessive strong reducing agent is dropwise added under the low-temperature stirring condition to ensure that the high hydrogen evolution overpotential elements are completely reduced, so that the porous active carbon composite material containing monodisperse atomic clusters is obtained.
Compared with the existing preparation method, the atomic cluster-level hydrogen evolution inhibiting metal contained in the unit area of the carbon material prepared by the preparation method has higher content concentration, more uniform dispersion and smaller size, and the diameter of the generated nano particles is about 1 nm. The binding force with the carbon material is higher, the utilization rate of inhibiting the hydrogen evolution agent can be greatly improved when the catalyst is applied to a lead-carbon battery, the poisoning cost is reduced, the water consumption in the use process of the battery is reduced, and the service life of the battery is prolonged.

Claims (8)

1. The active carbon composite material applied to the lead-carbon battery electrode can be prepared by the following method:
1) Preparing solution A:
blending the soluble salt of the high hydrogen evolution overpotential element and the high polymer water solution into the solution A in water; the mass concentration of the high molecular polymer aqueous solution is 20-60 wt%; wherein the concentration of the soluble salt of the high hydrogen evolution overpotential element in the solution A is 1-10mg/ml, and the mass ratio of the high polymer to the high hydrogen evolution overpotential element is 0.1-20:1, a step of;
2) Preparing slurry B:
dropwise adding the solution A to an activated carbon material while stirring into a slurry state B, wherein the ratio of the number of moles of the high hydrogen evolution overpotential element to the surface area of the carbon material is 1mmol:2000-30000m 2 ；
3) Placing the slurry B in a stirring state at the temperature of-4-4 ℃, dropwise adding a strong reducing agent solution with the concentration of 1-10g/L into the slurry B, continuously stirring for 0.5-24h after dropwise adding, wherein the strong reducing agent comprises the following components in a molar ratio of high hydrogen evolution overpotential elements of=1-30: 1
4) Drying for 1-24 hours at 60-120 ℃ to obtain a monodisperse atom cluster-activated carbon composite material;
the high molecular polymer is sodium polymethacrylate (PMAA-Na) and/or polyethylene glycol dimethacrylate;
the high hydrogen evolution overpotential element comprises one or more of indium, lead, zinc, gallium, cerium and bismuth.
2. A composite material according to claim 1, wherein:
the strong reducing agent solution is one or more than two of aqueous solutions of sodium borohydride with the mass concentration of 1-10g/L and hydrazine hydrate with the mass concentration of 1-10 g/L;
the soluble salt of the high hydrogen evolution overpotential element is one of soluble nitrate, sulfate, phosphate and chloride.
3. A composite material according to claim 1, wherein:
the size of the atomic clusters of the high hydrogen evolution overpotential element in the prepared monodisperse atomic cluster-active carbon composite material is 0.1-10nm.
4. A composite material according to claim 3, wherein:
the size of the atomic clusters of the high hydrogen evolution overpotential element in the prepared monodisperse atomic cluster-active carbon composite material is 0.1-5nm.
5. Use of the activated carbon composite material of any one of claims 1-4 in lead-carbon battery electrodes.
6. The use according to claim 5, wherein:
the lead-carbon battery electrode comprises the following materials in parts by weight: 500-800 parts of lead powder, 1-20 parts of the active carbon composite material of any one of claims 1-3, 6-10 parts of barium sulfate, and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
7. The use according to claim 5, wherein:
the preparation process of the lead-carbon battery electrode comprises the following steps: (1) According to parts by weight, premixing 500-800 parts of lead powder, 1-20 parts of the active carbon composite material according to any one of claims 1-3, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m by a high-speed mixer, adding 50-100 parts of deionized water into the premixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) Scraping the lead plaster on a metal lead grid, and solidifying and drying to obtain leadA carbon battery negative electrode; curing temperature of 30-50 o C, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 DEG o C, the time is 10-30 hours.
8. The use according to claim 7, characterized in that: the metal lead grid has the dimensions of 50-1000-mm long, 20-80-mm wide and 0.5-4-mm thick.
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