CN112310392A - Preparation method of high-bulk density porous carbon/lead composite material - Google Patents
Preparation method of high-bulk density porous carbon/lead composite material Download PDFInfo
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- CN112310392A CN112310392A CN202011206781.1A CN202011206781A CN112310392A CN 112310392 A CN112310392 A CN 112310392A CN 202011206781 A CN202011206781 A CN 202011206781A CN 112310392 A CN112310392 A CN 112310392A
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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
- H01M4/36—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
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a high-bulk density porous carbon/lead composite material. The composite material prepared by the method has high lead content which can reach more than 85 percent at most, has stacking density far higher than that of a carbon material, has small density difference with lead powder, is suitable for a lead-carbon battery, is easier to mix and disperse with the lead powder uniformly in a paste mixing process for preparing a negative plate, and can ensure the uniformity of the performance of the plate; the interface between the lead particles and the porous carbon particles in the composite material is tightly combined, and the interface resistance is low, so that the electronic conduction is facilitated, and the multiplying power characteristic of the lead-carbon battery is improved; lead is attached to the surfaces of large-size pores in the carbon material, so that the hydrogen evolution overpotential of the carbon material can be improved, and the negative hydrogen evolution side reaction in the battery charging process can be effectively inhibited; in addition, the preparation method does not need complex process equipment, does not have subsequent processes such as washing treatment and the like, has simple process flow, and is easy for large-scale production and application.
Description
Technical Field
The invention relates to a preparation method of a high-density porous carbon/lead composite material, belongs to the technical field of advanced battery materials, and is used for a lead-carbon battery cathode material.
Background
The lead-acid battery has the characteristics of easily available raw materials, low price, high reliability in application, wide environmental temperature range, suitability for heavy-current discharge and the like, and has absolute advantages in various chemical power supplies. The negative electrode of the lead-acid battery is gradually sulfated, and particularly, in the process of high-rate charge and discharge, the specific surface area and the porosity of a negative electrode active substance are reduced, so that the charge acceptance of the battery is reduced, and the battery finally loses efficacy.
The lead-carbon battery is a novel battery developed by applying a carbon electrode material of a super capacitor to a traditional lead-acid battery, integrates the characteristics of the super capacitor, can greatly improve the performance of the traditional lead-acid battery, particularly can effectively inhibit the sulfation of a negative electrode, and improves the service performance of the battery under the charge state of a large-current charge-discharge part. The lead-carbon battery adds the carbon material into the negative lead paste in an 'internal mixing' mode, does not change the structure of the traditional lead-acid battery, and is suitable for industrial mass production. At present, carbon materials applied in lead-carbon batteries are mainly activated carbon with developed pores; in addition, carbon nanotubes, graphene, acetylene black, and functional carbon materials modified with hydrogen evolution inhibitors and the like have many applications. The influence of different types and structures of carbon materials on the lead cathode and the performance of the lead carbon battery is very different. The mixing method of the lead powder, the carbon material and other additives is generally divided into dry mixing and wet mixing, wherein the former is to mix the lead powder and the carbon material with water and add acid to prepare a paste, and the latter is to mix the carbon material and the additives with water and add acid to prepare a suspension solution and then mix the suspension solution with the lead powder to prepare the paste. Because the specific gravity difference between the carbon material and the lead powder is too large, the carbon material and the lead powder are difficult to be uniformly mixed by the two methods, so that the carbon material is easily unevenly distributed in the solidified negative plate, the advantages of super capacitance property, high conductivity and the like of the carbon material cannot be effectively exerted, even the local hydrogen evolution of the negative electrode of the battery is aggravated, and the performance of the battery is reduced.
The compounding of carbon materials with lead is an important way to improve the application performance of the carbon materials. The Chinese patent application 201811538256.2 is to adsorb lead sources such as lead nitrate on the surface of the carbon material after oxidation treatment, and then obtain the nano lead/carbon composite material after high-temperature heat treatment. The composite material can well inhibit the hydrogen evolution reaction of the cathode of the lead-carbon battery, but the amount of the actually introduced lead is not high, and the density of the composite material is not remarkably changed compared with that of a basic carbon material. The Chinese patent application 201710849941.6 is to mix the carbon material and lead ion solution evenly, slowly drop-add precipitant such as sodium hydroxide solution, etc. to make lead ion deposit on the surface of carbon material completely, and then obtain the composite material by high temperature treatment. The lead deposition can reach 90%, but the high lead deposition causes the porous carbon material to be tightly coated by lead, which causes severe blockage of pores. The Chinese patent application 201210493085.2 firstly carries out surface modification treatment on activated carbon at high temperature, and then the lead-carbon composite material is prepared by a vacuum lead plating process, wherein the lead plating amount on the surface of the activated carbon is 30-80%. The method adopts a vacuum lead plating process, has high equipment requirement and complex process, and is not beneficial to large-scale production.
Disclosure of Invention
The invention aims to solve the problem of the prior art and provides a simple preparation method of a carbon/lead composite material, which can effectively improve the mixing uniformity of the carbon/lead composite material and lead powder, reduce the contact resistance between a lead material and a carbon material and obviously improve the performance of a lead-carbon battery.
The technical scheme adopted by the invention is that the preparation method of the high-density porous carbon/lead composite material comprises the following steps:
(1) adding 20-100 mu m porous carbon material and polyvinyl butyral into a stirring kettle according to the mass ratio of 1: 0.5-2.5, stirring and heating under normal pressure, heating to 100-200 ℃ to completely melt the polyvinyl butyral, vacuumizing the stirring kettle, stirring for 0.5-5 h under vacuum, allowing the molten polyvinyl butyral to enter pores of the porous carbon material, filling gas with 1-5 atmospheres into the stirring kettle, fully pressing the polyvinyl butyral into the pores, adding a solvent according to the mass ratio of 0.2-10 times of the dosage of the polyvinyl butyral, continuously stirring for 0.5-10 h at the temperature, filtering while hot, drying the filtered carbon material for 2-10 h under the vacuum condition of 120-250 ℃ and 100-5000 Pa, and removing the residual solvent.
(2) Mixing lead oxide powder with the particle size of 5-50 mu m and the porous carbon material treated in the step (1) according to the mass ratio of 1: 0.1-2, uniformly mixing, heating to 260-350 ℃ at the speed of 5-20 ℃/min in a flowing gas atmosphere, reacting for 0.1-10 h, heating to 500-600 ℃ at the speed of 20-60 ℃/min in a nitrogen or argon atmosphere, carrying out heat treatment for 0.1-2 h, completely removing polyvinyl butyral, rapidly cooling to below 200 ℃ to obtain the porous carbon/lead composite material, sieving the composite material by using a standard sieve with the mesh of 40-80, and crushing screen residues until the composite material is completely sieved.
The specific surface area of the porous carbon material is 800-2000 m2(ii) a total pore volume of 0.5 to 2.0cm3The proportion of mesopores is 50-90%, wherein 30-50nm mesopores are contained.
The polymerization degree of the polyvinyl butyral is 1000-3000.
And (2) vacuumizing the stirring kettle in the step (1) to reach the vacuum degree of 100-5000 Pa.
And (2) filling gas with 1-5 atmospheric pressures into the stirring kettle in the step (1) to be air, nitrogen or argon.
The solvent added in the step (1) is one or a mixture of two of propanol, butanol, n-pentanol, ethylene glycol, diacetone alcohol, benzyl alcohol, toluene, xylene, p-xylene, ethylene glycol monomethyl ether, butyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and cyclohexanone.
The oxidation degree of the lead oxide powder is 65-90%.
The flowing gas atmosphere in the step (2) is one of nitrogen, argon and a mixed gas of nitrogen or argon and carbon monoxide, and when the mixed gas is used, the partial pressure of the carbon monoxide is 0.1-2%.
And (3) cooling the composite material subjected to high-temperature treatment in the step (2) at a speed of 30-50 ℃/min.
The invention has the beneficial effects that:
(1) the porous carbon/lead composite material prepared by the method has high lead content, the stacking density is far higher than that of the carbon material, and the density difference with lead powder is greatly reduced; the lead oxide particles and the porous carbon particles are connected through simple substance lead which is reduced and melted and then solidified, the combination is tight and firm, the surface contact replaces the point contact between the common particles, the interface contact area is large, the lead conductivity at the interface is high, the contact resistance between the two particles is greatly reduced, and the electronic conductivity between the particles is greatly improved. The carbon powder-paste mixing and kneading device is suitable for being used in a negative electrode of a lead-carbon battery, is easier to be uniformly mixed in the process of mixing with lead powder and kneading paste, avoids the problems of poor internal uniformity of a negative plate and influence on the performance of the battery caused by overlarge density difference between the carbon material and the lead powder, and is favorable for reducing the internal resistance of a polar plate and improving the large-current charge and discharge performance of the battery.
(2) The method can well keep the original porous structure of the carbon material while realizing high lead content of the composite material, can fully play the role of high specific surface characteristic of the carbon material when the carbon material is used for the cathode of the lead-carbon battery, and meanwhile, a small amount of lead is attached to the surface of a larger pore in the pore recovery process of the carbon material, so that the hydrogen evolution overpotential of the carbon material can be improved, and the hydrogen evolution process of the cathode of the lead-carbon battery can be inhibited.
(3) The method completes the preparation of the composite material mainly through a heat treatment process, does not need complex process equipment, does not have post-treatment processes such as washing and the like, has simple process and is easy for large-scale preparation and production.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The specific surface area is 1000m2Adding 500g of porous carbon (60-100 mu m) and 500g of polyvinyl butyral with the polymerization degree of 1700-1800 into a stirring kettle, stirring and heating under normal pressure, vacuumizing the stirring kettle after heating to 130 ℃, stirring for 2 hours under the vacuum of 1000Pa, then filling air with 2 atmospheric pressures into the stirring kettle, adding 1000g of p-xylene, continuously stirring for 3 hours, filtering while hot, and drying the carbon material obtained after filtering for 5 hours under the vacuum conditions of 130 ℃ and 1000 Pa.
And uniformly mixing 1000g of lead oxide powder with the granularity of 30-50 mu m with the obtained porous carbon material, heating to 300 ℃ at the speed of 20 ℃/min in a flowing nitrogen atmosphere, reacting for 2h, heating to 500 ℃ at the speed of 50 ℃/min in the nitrogen atmosphere, carrying out heat treatment for 0.2h, rapidly cooling to below 200 ℃ to obtain the porous carbon/lead composite material, screening the composite material by using a 40-mesh standard sieve, and crushing screen residues until the composite material is completely screened. The lead content of the composite material is 62%.
Example 2
The specific surface area is 1800m2500g of porous carbon and 1000g of polyvinyl butyral with the polymerization degree of 1700-1800 are added into a stirring kettle, the mixture is stirred and heated under normal pressure, and the temperature is raised to150℃Vacuumizing the stirring kettle, stirring for 2h under 1000Pa, introducing high-purity nitrogen with 3 atm into the stirring kettle, adding 1500g of mixed solvent (1: 2) of n-amyl alcohol and ethylene glycol, stirring for 5h, filtering while hot, and drying the filtered carbon material for 5h under 1000Pa vacuum at 160 ℃.
Uniformly mixing 2000g of lead oxide powder with the granularity of 30-50 mu m with the obtained porous carbon material, heating to 320 ℃ at the speed of 20 ℃/min in a flowing nitrogen atmosphere, reacting for 0.5h, heating to 500 ℃ at the speed of 50 ℃/min in the nitrogen atmosphere, carrying out heat treatment for 0.2h, and rapidly cooling to below 200 ℃ to obtain the porous carbon/lead composite material with the lead content of 73.5%.
Example 3
The specific surface area is 1500m2Adding 500g of porous carbon and 800g of polyvinyl butyral with the polymerization degree of 2400-2500 into a stirring kettle, stirring and heating under normal pressure, heating to 190 ℃, vacuumizing the stirring kettle, stirring for 3 hours under the vacuum of 1000Pa, then filling high-purity nitrogen with the pressure of 5 atm into the stirring kettle, adding 3000g of dimethyl succinate, continuously stirring for 5 hours, filtering while hot, and drying the filtered carbon material for 5 hours under the vacuum conditions of 160 ℃ and 1000 Pa.
Uniformly mixing 750g of lead oxide powder with the granularity of 30-50 mu m with the obtained porous carbon material, heating to 280 ℃ at the speed of 20 ℃/min in the flowing atmosphere of carbon monoxide and nitrogen (the partial pressure of carbon monoxide is 1 percent), reacting for 2 hours, heating to 600 ℃ at the speed of 50 ℃/min in the nitrogen atmosphere, carrying out heat treatment for 0.2 hour, rapidly cooling to below 200 ℃ to obtain the porous carbon/lead composite material, sieving the composite material by using a 40-mesh standard sieve, and crushing screen residues until the screen residues completely pass the sieving. The lead content of the composite material is 51 percent.
Claims (9)
1. A preparation method of a high-density porous carbon/lead composite material is characterized by comprising the following steps:
(1) adding 20-100 mu m porous carbon material and polyvinyl butyral into a stirring kettle according to the mass ratio of 1: 0.5-2.5, stirring and heating under normal pressure, heating to 100-200 ℃ to completely melt the polyvinyl butyral, vacuumizing the stirring kettle, stirring for 0.5-5 h under vacuum, allowing the molten polyvinyl butyral to enter pores of the porous carbon material, filling gas with 1-5 atmospheres into the stirring kettle, fully pressing the polyvinyl butyral into the pores, adding a solvent according to the mass ratio of 0.2-10 times of the dosage of the polyvinyl butyral, continuously stirring for 0.5-10 h at the temperature, filtering while hot, drying the filtered carbon material for 2-10 h under the vacuum condition of 120-250 ℃ and 100-5000 Pa, and removing the residual solvent;
(2) mixing lead oxide powder with the particle size of 5-50 mu m and the porous carbon material treated in the step (1) according to the mass ratio of 1: 0.1-2, uniformly mixing, heating to 260-350 ℃ at the speed of 5-20 ℃/min in a flowing gas atmosphere, reacting for 0.1-10 h, heating to 500-600 ℃ at the speed of 20-60 ℃/min in a nitrogen or argon atmosphere, carrying out heat treatment for 0.1-2 h, completely removing polyvinyl butyral, rapidly cooling to below 200 ℃ to obtain the porous carbon/lead composite material, sieving the composite material by using a standard sieve with the mesh of 40-80, and crushing screen residues until the composite material is completely sieved.
2. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: ratio table of porous carbon materialThe area is 800-2000 m2(ii) a total pore volume of 0.5 to 2.0cm3The proportion of mesopores is 50-90%, wherein 30-50nm mesopores are contained.
3. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: the polymerization degree of the polyvinyl butyral is 1000-3000.
4. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: and (2) vacuumizing the stirring kettle in the step (1) to reach the vacuum degree of 100-5000 Pa.
5. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: and (1) filling gas with 1-5 atmospheric pressures into the stirring kettle, wherein the gas is air, nitrogen or argon.
6. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: the solvent added in the step (1) is one or a mixture of two of propanol, butanol, n-pentanol, glycol, diacetone alcohol, benzyl alcohol, toluene, xylene, p-xylene, ethylene glycol monomethyl ether, butyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and cyclohexanone.
7. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: the oxidation degree of the lead oxide powder is 65-90%.
8. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: the flowing gas atmosphere in the step (2) is nitrogen, argon, the mixture of nitrogen and carbon monoxide or the mixture of argon and carbon monoxide, and when the mixed gas is used, the partial pressure of carbon monoxide is 0.1-2%.
9. The method for preparing the high-density porous carbon/lead composite material according to claim 1, wherein the method comprises the following steps: and (3) cooling the composite material subjected to high-temperature treatment in the step (2) at a speed of 30-50 ℃/min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214245A (en) * | 2013-03-29 | 2013-07-24 | 中国科学院过程工程研究所 | Carbon/carbon composite microsphere material, production method and lithium ion battery |
| CN103482597A (en) * | 2012-06-14 | 2014-01-01 | 中国人民解放军63971部队 | Mesoporous-macroporous carbon production method |
| CN106587047A (en) * | 2016-12-12 | 2017-04-26 | 张家港智电芳华蓄电研究所有限公司 | Preparation method for nanoporous carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103482597A (en) * | 2012-06-14 | 2014-01-01 | 中国人民解放军63971部队 | Mesoporous-macroporous carbon production method |
| CN103214245A (en) * | 2013-03-29 | 2013-07-24 | 中国科学院过程工程研究所 | Carbon/carbon composite microsphere material, production method and lithium ion battery |
| CN106587047A (en) * | 2016-12-12 | 2017-04-26 | 张家港智电芳华蓄电研究所有限公司 | Preparation method for nanoporous carbon |
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