CN106531972B - Preparation method of lead-graphene composite material for lead-carbon battery - Google Patents

Preparation method of lead-graphene composite material for lead-carbon battery Download PDF

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CN106531972B
CN106531972B CN201610718669.3A CN201610718669A CN106531972B CN 106531972 B CN106531972 B CN 106531972B CN 201610718669 A CN201610718669 A CN 201610718669A CN 106531972 B CN106531972 B CN 106531972B
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lead
composite material
graphene composite
mixed solution
graphene
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CN106531972A (en
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李新禄
张艳艳
赵昱颉
粟泽龙
赵奚誉
王荣华
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Chongqing Jiabaoxiang Technology Co ltd
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Chongqing 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
    • H01M16/00—Structural combinations of different types of electrochemical generators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for 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
    • H01M4/14—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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
    • 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

Abstract

The invention provides a preparation method of a lead-graphene composite material for a lead-carbon battery, which is characterized in that the lead-graphene composite material is prepared by adopting simple methods such as liquid phase reaction, centrifugation, high-temperature sintering and the like, the process is simple, the production efficiency is high, the large-scale production can be realized, and the popularization and the application are convenient. The obtained lead-graphene composite material has high hydrogen evolution overpotential, the problem of low hydrogen evolution overpotential of graphene is well solved, and the capacitance performance of graphene is improved. The composite material used as an additive of the negative electrode of the lead-carbon battery can effectively improve the rate capability, the charge acceptance and the HRPSOC cycle life of the battery, reduce the water loss of the lead-carbon battery and has wide application prospect.

Description

Preparation method of lead-graphene composite material for lead-carbon battery
Technical Field
The invention belongs to the technical field of graphene application, and particularly relates to a preparation method of a lead-graphene composite material for a lead-carbon battery.
Background
In 2004, physicists of the university of manchester, england succeeded in isolating graphene from graphite, which had a perfect two-dimensional crystal structure with a hexagonal lattice of six carbon atoms and a thickness of one atomic layer. Between carbon atoms bySigma bond connected in sp 2 Hybridized, these sigma bonds confer extremely excellent mechanical properties and structural rigidity to graphene. In graphene, each carbon atom has an unbound p electron, and these p electrons can move freely in the crystal, which gives graphene good conductivity. Due to the characteristics of high conductivity, high strength, ultra-light weight and the like of the graphene, the graphene has wide application prospects in the fields of solar cells, sensors, nanoelectronics, high-performance nanoelectronic devices, gas sensors, energy storage and the like, and becomes a research hotspot in recent years.
The lead-carbon battery is a novel super battery, and integrates a lead-acid battery and a super capacitor: the advantages of instantaneous high-capacity charging of the super capacitor and the specific energy of the lead-acid battery are exerted, and the lead-acid battery has good charging and discharging performance. The graphene is introduced into the negative electrode material of the lead-carbon battery, so that the negative electrode sulfation phenomenon is prevented, and the HRPSoC cycle life and the charging acceptance of the battery are improved. However, the hydrogen evolution overpotential of graphene is low, so that the problem of hydrogen evolution of the negative electrode is aggravated, the water loss of the storage battery is serious, and the maintenance-free performance is reduced. The existence of the problem limits the application of the lead-carbon battery in a wider range and a wider field.
Disclosure of Invention
The invention aims to solve the defects and shortcomings of the prior art and provides a method for preparing a lead-graphene composite material for a lead-carbon battery through a simple chemical synthesis method. The lead-graphene composite material is prepared by adopting simple methods such as liquid phase reaction, centrifugation, high-temperature sintering and the like, the process is simple, the obtained lead-graphene has high hydrogen evolution overpotential, and the problem of low hydrogen evolution overpotential of the graphene is well solved.
The technical route of the invention is as follows: the lead-graphene composite material is prepared by taking graphene and lead nitrate or lead acetate as raw materials through a chemical reaction, and then the prepared lead-graphene composite material is added into a negative electrode of a lead-carbon battery.
1) A preparation method of a lead-graphene composite material for a lead-carbon battery is characterized by comprising the following steps:
1.1) dissolving soluble lead salt into deionized water according to a certain mass-volume ratio to obtain a mixed solution A;
1.2) uniformly dispersing graphene into the mixed solution A prepared in the step 1.1) according to a certain mass-to-volume ratio to obtain a mixed solution B;
1.3) adding an alkali solution with a certain concentration into the mixed solution B prepared in the step 1.2) according to a certain volume ratio to obtain a mixed solution C;
1.4) centrifugally separating the mixed solution C prepared in the step 1.3), collecting precipitates, and repeatedly washing with a washing solution until the centrifugal solution is neutral (namely the pH value reaches 7) to obtain a solid residue;
1.5) carrying out freeze drying on the residue prepared in the step 1.4) to obtain a precursor of the lead-graphene composite material;
1.6) heating the lead-graphene composite material precursor prepared in the step 1.5) to a certain temperature in an inert atmosphere, preserving heat for a certain time, cooling to room temperature, and taking out to obtain the final lead-graphene composite material.
The soluble lead salt in the step 1.1) is one or two of lead nitrate and lead acetate, and the mass volume ratio of the soluble lead salt to deionized water is 0.1-0.5 g: 100 ml;
the average particle size of the graphene in the step 1.2) is 5-35 mu m, and the specific surface area is 500-1200 m 2 The number of layers is 2-10, and the mass volume ratio of the graphene to the mixed solution A is 0.05-1.00 g: 100 ml;
the alkaline solution in the step 1.3) is NaOH, KOH or Na 2 CO 3 、NaHCO 3 One or more of ammonia water and the alkaline solution, wherein the pH value of the alkaline solution is 8-14, and the volume ratio of the alkaline solution to the mixed solution B is 1-10 ml: 100 ml;
the centrifugal rotating speed in the step 1.4) is 2000-5000 r/min, the centrifugal time is 3-15 min, and the used washing solution is one or two of deionized water and ethanol;
the freeze drying temperature in the step 1.5) is-50 to-80 ℃, the vacuum degree is 1 to 20Pa, basic lead carbonate contained in a precursor of the lead-graphene composite material is in a regular hexagon shape, and the average particle size is 500 to 900 nm;
the inert atmosphere in the step 1.6) is argon or nitrogen, the heating is carried out to 300-500 ℃, the heat preservation time is 1-3h, and the prepared lead-graphene composite material is used as a lead-carbon electrode negative electrode material, wherein the addition amount of the lead-graphene composite material is 0.1-1.0% of the mass of lead powder in the negative electrode.
2) The preparation method of the lead-carbon battery cathode is characterized by comprising the following steps:
2.1) weighing the above materials according to the mass ratio of 90-100 g of lead powder, sulfuric acid, barium sulfate, short fibers, lead-graphene composite material, lignin, humic acid and deionized water to 8.5-10 g of composite material, 0.5-1.0 g of composite material, 0.1-0.15 g of composite material, 0.1-1.0 g of composite material, 0.1-0.3 g of composite material and 10-15 g of composite material, wherein the density of sulfuric acid is 1.24-1.28 g/cm 3 ；
2.2) uniformly dispersing the lead-graphene composite material in the step 2.1) into the deionized water in the step 2.1) to obtain a mixed solution D;
2.3) dry-mixing the barium sulfate, the lead-graphene composite material, the short fibers, the lignin, the humic acid and the lead powder in the step 2.1) for 5-10 min to obtain a mixture A;
2.4) adding the mixed solution D prepared in the step 2.2) into the mixture A prepared in the step 2.3), and quickly stirring for 5-10 min to obtain a mixture B;
2.5) adding the sulfuric acid obtained in the step 2.1) into the mixture B within 5min, and quickly stirring to obtain negative lead plaster;
2.6) quickly coating the lead plaster obtained in the step 2.5) on a negative plate grid, wherein the curing temperature of a polar plate is 40-60 ℃, the humidity is 60% -99%, the time is 24-48 h, the drying temperature is 40-60 ℃, and the time is 12-24 h, so that the negative plate of the lead-carbon battery is finally obtained.
After the technical scheme is adopted, the invention mainly has the following effects:
1. the method adopts liquid phase reaction, centrifugation and simple chemical reaction to prepare the lead-graphene composite material, has simple process, convenient operation and high production efficiency, is beneficial to realizing large-scale production and is convenient for popularization and application;
2. the lead-graphene composite material prepared by the invention overcomes the defect of low hydrogen evolution overpotential of graphene, and reduces the water loss of a lead-carbon battery.
3. The lead-graphene composite material prepared by the invention improves the capacitance performance of graphene, and the capacity of a battery is improved by adding the graphene composite material into a lead-carbon battery.
4. After the lead-graphene composite material prepared by the invention is added into a lead-carbon battery cathode, the rate performance, the charge acceptance and the HRPSOC cycle life of the lead-carbon battery are improved.
Drawings
Fig. 1 is an SEM image of the lead-graphene composite precursor for a lead-carbon battery prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
1) A preparation method of a lead-graphene composite material for a lead-carbon battery is disclosed, wherein the preparation method comprises the following steps:
1.1) adding soluble lead salt into deionized water, and preparing according to the ratio of the soluble lead salt to the deionized water of 0.1g to 100ml to obtain a mixed solution A, wherein the soluble lead salt is lead nitrate;
1.2) adding graphene into the mixed solution A, and preparing according to the ratio of 0.05g to 100ml of graphene to the mixed solution A to obtain a mixed solution B;
1.3) adding an alkali solution into the mixed solution B, and preparing according to the ratio of the alkali solution to the mixed solution B of 1ml to 100ml to obtain a mixed solution C, wherein the alkali solution is a NaOH solution, and the pH value is 14;
1.4) carrying out centrifugal separation on the mixed solution C prepared in the step 3, collecting precipitate, washing with a washing solution until the centrifugal solution reaches neutrality (namely pH reaches 7) to obtain solid residue, wherein the washing solution is deionized water, the rotation speed is 2000r/min during centrifugation, and the centrifugation time is 15 min;
1.5) carrying out freeze drying on the solid residue prepared in the step 4 to obtain a precursor of the lead-graphene composite material, wherein the freeze drying condition is-80 ℃ and 10 Pa;
1.6) heating the precursor of the lead-graphene composite material prepared in the step 5 to 300 ℃ in the protective atmosphere of nitrogen, preserving heat for 3 hours, cooling to room temperature, and taking out to obtain the lead-graphene composite material.
2) The preparation method of the lead-carbon battery cathode comprises the following steps:
2.1) weighing the above materials according to the mass ratio of 90g to 8.5g to 0.5g to 0.05g to 0.1g to 10g of lead powder to sulfuric acid to barium sulfate to short fiber to lead-graphene composite material to lignin to humic acid to deionized water, wherein the density of the sulfuric acid is 1.24g/cm 3 ；
2.2) uniformly dispersing the lead-graphene composite material in the step 2.1) into the deionized water in the step 2.1) to obtain a mixed solution D;
2.3) dry-mixing the barium sulfate, the lead-graphene composite material, the short fibers, the lignin, the humic acid and the lead powder in the step 2.1) for 5min to obtain a mixture A;
2.4) adding the mixed solution D prepared in the step 2.2) into the mixed material A prepared in the step 2.3), and quickly stirring for 5min to obtain a mixed material B;
2.5) adding the sulfuric acid obtained in the step 2.1) into the mixture B within 5min, and quickly stirring to obtain negative lead plaster;
2.6) quickly coating the lead plaster obtained in the step 2.5) on a negative plate grid, wherein the curing temperature of the plate is 40 ℃, the humidity is 60%, the time is 24 hours, the drying temperature is 40 ℃, and the time is 12 hours, and finally the negative plate of the lead-carbon battery is obtained.
Example 2
1) A preparation method of a lead-graphene composite material for a lead-carbon battery, which is the same as in embodiment 1, wherein:
the soluble lead salt in the step 1.1) is lead nitrate, and the mixed solution A is prepared according to the proportion of the lead nitrate to the deionized water of 0.25g to 100 ml;
the mixed solution B in the step 1.2) is prepared according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step 1.3) is prepared according to the ratio of 5ml of alkali solution to 100ml of mixed solution B, wherein the alkali solution is KOH solution, and the pH value is 10;
the washing liquid in the step 1.4) is absolute ethyl alcohol, the centrifugal rotating speed is 5000r/min during centrifugation, and the centrifugation time is 3 min;
the freeze drying temperature in the step 1.5) is-70 ℃, and the vacuum degree is 10 Pa;
the protective atmosphere in the step 1.6) is argon, the heating temperature is 500 ℃, and the heat preservation time is 1 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 100g, 10g, 1.0g, 0.15g, 1.0g, 0.3g and 15g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.28g/cm 3 ；
The dry mixing time in the step 2.3) is 10 min;
the rapid stirring time in the step 2.4) is 10 min;
the curing temperature of the polar plate in the step 2.6) is 60 ℃, the humidity is 99%, the time is 48 hours, the drying temperature is 60 ℃, and the time is 24 hours.
Example 3
1) A preparation method of a lead-graphene composite material for a lead-carbon battery, which is the same as in embodiment 1, wherein:
the soluble lead salt in the step (1) is lead nitrate, and the mixed solution A is prepared according to the proportion of the lead nitrate to deionized water of 0.25g to 100 ml;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of the alkali solution to the mixed solution B of 10ml to 100ml, wherein the alkali solution is Na 2 CO 3 A solution having a pH of 8;
the washing liquid in the step (4) is absolute ethyl alcohol, the centrifugal speed is 4000r/min during centrifugation, and the centrifugation time is 8 min;
the freeze drying temperature in the step (5) is-50 ℃, and the vacuum degree is 20 Pa;
and (5) taking nitrogen as protective atmosphere in the step (6), heating at 500 ℃, and keeping the temperature for 1 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 95g, 9g, 0.75g, 0.1g, 0.6g, 0.2g and 12.5g, and the density of the sulfuric acid is 1.26g/cm 3 ；
The dry mixing time in the step 2.3) is 7 min;
the rapid stirring time in the step 2.4) is 7 min;
the curing temperature of the polar plate in the step 2.6) is 50 ℃, the humidity is 85%, the time is 36h, the drying temperature is 50 ℃, and the time is 18 h.
Example 4
1) The preparation method of the lead-graphene composite material for the lead-carbon battery is the same as the embodiment 1, wherein:
the soluble lead salt in the step (1) is lead acetate, and the mixed solution A is prepared according to the ratio of the lead acetate to the deionized water of 0.1g to 100 ml;
preparing the mixed solution B in the step (2) according to the ratio of 0.05g of graphene to 100ml of the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of 5ml of aqueous alkali to 100ml of mixed solution B, wherein the aqueous alkali is ammonia water, and the pH value is 10;
the washing liquid in the step (4) is deionized water, the centrifugal rotating speed is 2000r/min during centrifugation, and the centrifugation time is 15 min;
the freeze drying temperature in the step (5) is-50 ℃, and the vacuum degree is 20 Pa;
and (5) taking nitrogen as protective atmosphere in the step (6), heating at 500 ℃, and keeping the temperature for 1 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 90g, 8.5g, 0.5g, 0.05g, 0.1g and 10g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.28g/cm 3 ；
The dry mixing time in the step 2.3) is 10 min;
the rapid stirring time in the step 2.4) is 10 min;
the curing temperature of the polar plate in the step 2.6) is 60 ℃, the humidity is 99%, the time is 48 hours, the drying temperature is 60 ℃, and the time is 24 hours.
Example 5
1) The preparation method of the lead-graphene composite material for the lead-carbon battery is the same as the embodiment 1, wherein:
the soluble lead salt in the step (1) is lead acetate, and the mixed solution A is prepared according to the ratio of the lead acetate to deionized water of 0.5g to 100 ml;
preparing the mixed solution B in the step (2) according to the ratio of the graphene to the mixed solution A of 1.0g to 100 ml;
the mixed solution C in the step (3) is prepared according to the ratio of the alkali solution to the mixed solution B of 7ml to 100ml, wherein the alkali solution is NaHCO 3 A solution having a pH of 12;
the washing liquid in the step (4) is absolute ethyl alcohol, the centrifugal rotating speed is 3000r/min during centrifugation, and the centrifugation time is 5 min;
the freeze drying temperature in the step (5) is-80 ℃, and the vacuum degree is 20 Pa;
and (4) adopting argon as protective atmosphere in the step (6), heating at 300 ℃, and keeping the temperature for 3 hours.
2) The preparation of the negative plate of the lead-carbon battery is the same as the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 100g, 10g, 1.0g, 0.15g, 1.0g, 0.3g and 15g, and the materials are weighed, wherein the sulfuric acid isDensity of 1.28g/cm 3 ；
The dry mixing time in the step 2.3) is 10 min;
the rapid stirring time in the step 2.4) is 10 min;
the curing temperature of the polar plate in the step 2.6) is 60 ℃, the humidity is 99%, the time is 48h, the drying temperature is 60 ℃, and the time is 24 h.
Example 6
1) A preparation method of a lead-graphene composite material for a lead-carbon battery, which is the same as in embodiment 1, wherein:
the soluble lead salt in the step (1) is lead acetate, and the mixed solution A is prepared according to the ratio of the lead acetate to deionized water of 0.25g to 100 ml;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of 5ml of alkali solution to 100ml of mixed solution B, wherein the alkali solution is NaOH solution, and the pH value is 8;
the washing liquid in the step (4) is absolute ethyl alcohol, the centrifugal rotating speed is 4000r/min during centrifugation, and the centrifugation time is 10 min;
the freeze drying temperature in the step (5) is-50 ℃, and the vacuum degree is 10 Pa;
and (4) adopting argon as protective atmosphere in the step (6), heating at 400 ℃, and keeping the temperature for 1.5 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 95g, 9g, 0.75g, 0.1g, 0.6g, 0.2g and 12.5g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.26g/cm 3 ；
The dry mixing time in the step 2.3) is 7 min;
the rapid stirring time in the step 2.4) is 7 min;
the curing temperature of the polar plate in the step 2.6) is 50 ℃, the humidity is 85%, the time is 36h, the drying temperature is 50 ℃, and the time is 18 h.
Example 7
1) The preparation method of the lead-graphene composite material for the lead-carbon battery is the same as the embodiment 1, wherein:
the soluble lead salt in the step (1) is a mixture of lead nitrate and lead acetate, and the mixed solution A is prepared according to the proportion of 0.25g of lead nitrate to 0.25g of lead acetate to 100ml of deionized water;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of 1ml of alkaline solution to 100ml of mixed solution B, wherein the alkaline solution is a mixed solution of KOH and NaOH, and the pH value is 14;
the washing liquid in the step (4) is a mixed solution of absolute ethyl alcohol and deionized water, the mixed solution is prepared according to the proportion of the absolute ethyl alcohol to the deionized water of 50ml to 50ml, the centrifugal rotating speed is 2000r/min during centrifugation, and the centrifugation time is 15 min;
the freeze drying temperature in the step (5) is-80 ℃, and the vacuum degree is 10 Pa;
and (4) adopting nitrogen as protective atmosphere in the step (6), heating at 300 ℃, and keeping the temperature for 3 hours.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 90g, 8.5g, 0.5g, 0.05g, 0.3g, 0.1g and 10g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.26g/cm 3 ；
The dry mixing time in the step 2.3) is 5 min;
the rapid stirring time in the step 2.4) is 5 min;
the curing temperature of the polar plate in the step 2.6) is 40 ℃, the humidity is 75%, the time is 36h, the drying temperature is 50 ℃, and the time is 24 h.
Example 8
1) A preparation method of a lead-graphene composite material for a lead-carbon battery, which is the same as in embodiment 1, wherein:
the soluble lead salt in the step (1) is a mixture of lead nitrate and lead acetate, and the mixed solution A is prepared according to the proportion of 0.1g of lead nitrate to 0.2g of lead acetate to 100ml of deionized water;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A, and performing ultrasonic dispersion for 1;
the mixed solution C in the step (3) is prepared according to the ratio of alkali solution to mixed solution B of 5ml to 100ml, wherein the alkali solution is the mixed solution of KOH and ammonia water, and the pH value is 10;
the washing liquid in the step (4) is a mixed solution of absolute ethyl alcohol and deionized water, and is prepared according to the proportion of the absolute ethyl alcohol to the deionized water of 70ml to 30ml, the centrifugal rotating speed is 4000r/min during centrifugation, and the centrifugation time is 10 min;
the freeze drying temperature in the step (5) is-65 ℃, and the vacuum degree is 15 Pa;
and (4) the protective atmosphere in the step (6) is argon gas, the heating temperature is 400 ℃, and the heat preservation time is 2 hours.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 100g, 10g, 1.0g, 0.15g, 1.5g, 0.3g and 15g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.28g/cm 3 ；
The dry mixing time in the step 2.3) is 7 min;
the rapid stirring time in the step 2.4) is 7 min;
the curing temperature of the polar plate in the step 2.6) is 60 ℃, the humidity is 99%, the time is 48 hours, the drying temperature is 60 ℃, and the time is 24 hours.
Example 9
1) A preparation method of a lead-graphene composite material for a lead-carbon battery, which is the same as in embodiment 1, wherein:
the soluble lead salt in the step (1) is a mixture of lead nitrate and lead acetate, and the mixed solution A is prepared according to the proportion of 0.2g to 0.3g to 100ml of lead nitrate to 0.3g to deionized water;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of alkali solution to mixed solution B of 10ml to 100ml, wherein the alkali solution is the mixed solution of KOH and NaHCO3, and the pH value is 8;
the washing liquid in the step (4) is a mixed solution of absolute ethyl alcohol and deionized water, the mixed solution is prepared according to the proportion of the absolute ethyl alcohol to the deionized water of 30ml to 70ml, the centrifugal rotating speed is 2000r/min during centrifugation, and the centrifugation time is 15 min;
the freeze drying temperature in the step (5) is-80 ℃, and the vacuum degree is 10 Pa;
and (4) adopting nitrogen as protective atmosphere in the step (6), heating at 500 ℃, and keeping the temperature for 1 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 90g, 8.5g, 0.5g, 0.05g, 0.2g, 0.1g and 10g, and the above materials are weighed, wherein the density of the sulfuric acid is 1.24g/cm 3 ；
The dry mixing time in the step 2.3) is 7 min;
the rapid stirring time in the step 2.4) is 7 min;
the curing temperature of the polar plate in the step 2.6) is 60 ℃, the humidity is 85%, the time is 48 hours, the drying temperature is 60 ℃, and the time is 24 hours.
Example 10
1) The preparation method of the lead-graphene composite material for the lead-carbon battery is the same as the embodiment 1, wherein:
the soluble lead salt in the step (1) is a mixture of lead nitrate and lead acetate, and the mixed solution A is prepared according to the proportion of 0.4g of lead nitrate to 0.1g of lead acetate to 100ml of deionized water;
preparing the mixed solution B in the step (2) according to the ratio of 0.5g to 100ml of graphene to the mixed solution A;
the mixed solution C in the step (3) is prepared according to the ratio of 3ml of alkaline solution to 100ml of mixed solution B, wherein the alkaline solution is KOH and Na 2 CO 3 The pH value of the mixed solution of (1) is 14;
the washing liquid in the step (4) is a mixed solution of absolute ethyl alcohol and deionized water, and is prepared according to the proportion of the absolute ethyl alcohol to the deionized water of 30ml to 70ml, the centrifugal rotating speed is 2000r/min during centrifugation, and the centrifugation time is 15 min;
the freeze drying temperature in the step (5) is-80 ℃, and the vacuum degree is 10 Pa;
and (4) adopting nitrogen as protective atmosphere in the step (6), heating at 500 ℃, and keeping the temperature for 1 h.
2) The preparation of the negative electrode of the lead-carbon battery is the same as that of the embodiment 1, wherein:
the mass ratio of the lead powder, the sulfuric acid, the barium sulfate, the short fibers, the lead-graphene composite material, the lignin, the humic acid and the deionized water in the step 2.1) is 95g, 9g, 0.75g, 0.1g, 1.0g, 0.2g and 12.5g, and the density of the sulfuric acid is 1.26g/cm 3 ；
The dry mixing time in the step 2.3) is 7 min;
the rapid stirring time in the step 2.4) is 7 min;
the curing temperature of the polar plate in the step 2.6) is 40 ℃, the humidity is 60%, the time is 48 hours, the drying temperature is 50 ℃, and the time is 24 hours.

Claims (6)

1. The preparation method of the lead-graphene composite material used as the negative electrode additive of the lead-carbon battery is characterized by comprising the following steps of:
(1) dissolving soluble lead salt into deionized water according to a certain mass-volume ratio to obtain a mixed solution A;
(2) uniformly dispersing graphene into the mixed solution A prepared in the step (1) according to a certain mass-volume ratio to obtain a mixed solution B;
(3) adding an alkali solution with a certain concentration into the mixed solution B prepared in the step (2) according to a certain volume ratio to obtain a mixed solution C; the alkali solution is NaOH, KOH or Na 2 CO 3 、NaHCO 3 One or more of ammonia water;
(4) centrifuging the mixed solution C prepared in the step (3), collecting precipitates, and then repeatedly washing with a washing solution until the centrifugal solution is neutral to obtain a solid residue;
(5) freeze-drying the solid residue prepared in the step (4) to obtain a precursor of the lead-graphene composite material; the freeze-drying temperature is-50 to-80 ℃, the vacuum degree is 1 to 20Pa, basic lead carbonate contained in a precursor of the lead-graphene composite material is in a regular hexagon shape, and the average particle size is 500 to 900 nm;
(6) heating the precursor of the lead-graphene composite material prepared in the step (5) to 300-500 ℃ in an inert atmosphere, preserving heat for 1-3h, cooling to room temperature, and taking out to obtain a final product, namely the lead-graphene composite material used as a lead-carbon battery cathode additive;
the use method of the lead-graphene composite material as the negative electrode additive of the lead-carbon battery comprises the following steps:
1) according to the lead powder: sulfuric acid: barium sulfate: short fiber: lead-graphene composite material: lignin: humic acid: the mass ratio of the deionized water is 90-100 g: 8.5-10 g: 0.5-1.0 g: 0.05-0.15 g: 0.1-1.0 g: 0.1-0.3 g: 0.1-0.3 g: weighing the above materials in 10-15 g, wherein the density of sulfuric acid is 1.24-1.28 g/cm 3 ；
2) Uniformly dispersing the lead-graphene composite material in the step 1) into the deionized water in the step 1) to obtain a mixed solution D;
3) dry-mixing the barium sulfate, the lead-graphene composite material, the short fibers, the lignin, the humic acid and the lead powder in the step 1) for 5-10 min to obtain a mixture A;
4) adding the mixed solution D obtained in the step 2) into the mixed material A, and quickly stirring for 5-10 min to obtain a mixed material B;
5) adding the sulfuric acid obtained in the step 1) into the mixture B within 5min, and quickly stirring to obtain negative lead plaster;
6) and (3) quickly coating the lead plaster in the step 5) on a negative plate grid, wherein the curing temperature of a polar plate is 40-60 ℃, the humidity is 60-99%, the time is 24-48 h, the drying temperature is 40-60 ℃, and the time is 12-24 h, so that the negative electrode of the lead-carbon battery is finally obtained.
2. The preparation method of the lead-graphene composite material as claimed in claim 1, wherein the soluble lead salt in the step (1) is one or both of lead nitrate and lead acetate, and the mass-to-volume ratio of the soluble lead salt to deionized water is 0.1-0.5 g: 100 ml.
3. The method for preparing the lead-graphene composite material as claimed in claim 1, wherein the graphene in the step (2) has an average particle size of 5 to 35 μm and a specific surface area of 500 to 1200m 2 The number of layers is 2-10, and the mass volume ratio of the graphene to the mixed solution A is 0.05-1.00 g: 100 ml.
4. The preparation method of the lead-graphene composite material as claimed in claim 1, wherein the pH value of the alkaline solution in the step (3) is 8 to 14, and the volume ratio of the alkaline solution to the mixed solution B is 1 to 10 ml: 100 ml.
5. The method for preparing the lead-graphene composite material as claimed in claim 1, wherein the centrifugation time in the step (4) is 3-15 min, the centrifugation rotation speed is 2000-5000 r/min, and the washing solution is one of deionized water or ethanol.
6. The method for preparing a lead-graphene composite material according to claim 1, wherein the inert atmosphere in the step (6) is argon or nitrogen.
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