CN110212172B - Carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material and preparation method thereof - Google Patents
Carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material and preparation method thereof Download PDFInfo
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- 239000005355 lead glass Substances 0.000 title claims abstract description 55
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 230000008021 deposition Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 239000000243 solution Substances 0.000 claims description 32
- 238000000926 separation method Methods 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 22
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- 229910021641 deionized water Inorganic materials 0.000 claims description 16
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- 239000002041 carbon nanotube Substances 0.000 claims description 6
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- 239000011261 inert gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
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- 238000000151 deposition Methods 0.000 abstract description 8
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- 239000002253 acid Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 4
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- 238000004070 electrodeposition Methods 0.000 description 2
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- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
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- 150000001621 bismuth Chemical class 0.000 description 1
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 150000002258 gallium Chemical class 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/36—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
- 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
-
- 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
-
- 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
-
- 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 carbon material in-situ deposition nano lead crystal grain/lead oxide composite material and a preparation method thereof. The method has the advantages of simple process, convenient operation, low production cost, contribution to realizing large-scale production and convenience for popularization and application; the product prepared by the method has the characteristics of high conductivity, high hydrogen evolution overpotential, high capacitance, excellent electrochemical performance and the like. The method can be widely used for chemical power supplies such as lead-carbon batteries, lithium ion batteries, super capacitors and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a carbon material in-situ deposition nano lead crystal grain/lead oxide composite material and a preparation method thereof.
Background
Lead-acid batteries have been developed for over 150 years, and have the advantages of readily available raw materials, low price, good safety performance, high recovery rate and the like, so that the lead-acid batteries are widely applied to electric energy supply and energy storage devices in various economic fields such as electric power, communication, military, traffic, navigation, aviation and the like. However, the active material specific surface area of the traditional negative plate of the lead-acid battery is small, the rapid charging is difficult, the plate is made to lose efficacy by sulfation easily under the HRPSoC working condition, the cycle life of the battery is greatly reduced, and the development of the lead-acid battery lags behind other high-performance novel batteries. The lead-carbon battery is a novel lead-acid battery with a carbon material with high specific surface, high specific power, high conductivity and long cycle life as a negative electrode additive. The lead-carbon battery introduces the carbon material into the negative electrode material of the lead-acid battery, so that the negative electrode sulfation phenomenon can be effectively prevented, and the HPRSOC cycle life and the charge acceptance of the battery are improved. However, the overpotential of hydrogen evolution of the carbon material is low, so that the negative electrode can generate violent hydrogen evolution reaction in the later charging period of the battery, so that the battery loses water seriously, and the battery fails.
In the prior art, patent publication No. CN104505262A discloses a method for depositing lead on graphene by electrodeposition to obtain a lead graphene composite material, and adding the material into lead powder to obtain a negative plate. Although the graphene is modified, the mixing performance of the graphene and the graphene can be improved, the effective contact area of the lead active substance and the graphene is small, the lead active substance and the graphene are not tightly combined, the charge and discharge performance, the power density and the cycle life of the battery are not remarkably improved, and the hydrogen evolution reaction and the water loss caused by the graphene are not effectively inhibited. And the early-stage production process of the technology is complex, the industrialization is difficult to realize, the electrodeposition waste liquid has great pollution to the environment, and the environmental protection cost is high. Another prior art patent publication No. CN102306784A discloses loading In on activated carbon by a ball milling method or a solvent precipitation method2O3、Bi2O3、Ga2O3The hydrogen evolution overpotential of the modified activated carbon is improved by taking one or a mixture of a plurality of the active carbon as a hydrogen evolution inhibitor. However, the hydrogen evolution inhibitor cannot be uniformly supported on the carbon material by a simple mechanical mixing method, the obtained supported material has a large particle size, is easy to agglomerate, and cannot effectively play the role of the hydrogen evolution inhibitor, such additives adversely affect the self-discharge of the battery, and the recycling of the lead negative electrode also increases the production cost.
For example, in a patent of 'a core-shell structure activated carbon negative electrode material of a lead-carbon battery and a preparation method thereof' with publication number CN108598429A published in 2018, 9, 28, the disclosed composite material is in a spherical shell-core structure, the shell of the spherical shell-core structure is activated carbon, and the core is a solid solution formed by bismuth salt-gallium salt. The preparation method comprises the steps of dissolving an organic carbon source in deionized water to form a mixed solution, adding the mixed solution into a reaction kettle, adding a bismuth salt-gallium salt to form a solid solution, filtering, washing and vacuum drying after the high-temperature and high-pressure reaction is finished, carbonizing in a protective gas atmosphere at constant temperature, and naturally cooling to obtain the product. The main disadvantages of this patent are: (1) the obtained core-shell structure activated carbon composite material contains non-lead (bismuth and gallium) elements, so that the self-discharge reaction of the lead-carbon battery is increased, and the recycling cost of the lead cathode is increased; (2) the raw material cost is high, and the used bismuth salt and gallium salt must be bismuth nitrate and gallium nitrate; (3) in the preparation method, the solid solution formed by the bismuth salt-gallium salt needs to be sintered by microwaves in the atmosphere of water vapor and carbon dioxide, the preparation conditions are harsh, the process route is complex, the yield is low, and the large-scale industrial production is not facilitated.
Disclosure of Invention
The invention aims to solve the defects and shortcomings of the prior art, and provides a composite material of carbon material in-situ deposited nano lead crystal grains/lead oxide and a preparation method thereof, wherein the composite material has the characteristics of simple process, convenience in operation, low production cost and the like, the composite material has the characteristics of high hydrogen evolution potential, high conductivity, high capacitance and the like, and when the obtained composite material is added into a lead cathode, the HRPSoC cycle life of a lead-carbon battery can be prolonged by at least 5 times, the charging efficiency is improved by 1.6 times, and the water loss is only 0.1g/Ah and is far lower than 1g/Ah (GB/T5008.1-2013) of the national standard.
The technical scheme for realizing the purpose of the invention is as follows: a carbon material in-situ deposited nano-lead crystal grain/lead oxide composite material is a carbon material surface in-situ deposited nano-lead crystal grain/lead oxide composite material. The material comprises the following components in percentage by mass:
10 to 90 percent of carbon material
80-5% of nano lead crystal grains
10 to 5 percent of lead oxide
Wherein: the carbon material is carbon nano tube or active carbon or carbon nano fiber or graphene nano sheet or graphite oxide, and the carbon content is at least more than 90%; the grain size of the nano lead crystal grains is 30-500 nm; the particle size of the lead oxide is 10-300 nm.
A method for preparing a carbon material in-situ deposited nano-lead crystal grain/lead oxide composite material is characterized in that a carbon material, soluble lead salt and an alkali solution are used as raw materials, and a product is obtained through simple processes of mixing and stirring, liquid phase reaction, solid-liquid separation, washing, drying and sintering. The method comprises the following specific steps:
(1) according to the mass (g) of the soluble lead salt: dissolving soluble lead salt into deionized water at a volume (ml) ratio of 0.1-0.6: 500, and fully stirring to obtain a mixed solution A;
(2) mass (g) of the carbon material: uniformly dispersing a carbon material into the mixed solution A at a volume (ml) ratio of 1:500, and mixing and stirring at room temperature for 10-30 minutes to obtain a mixed solution B of the carbon material and soluble lead salt;
wherein: the carbon material is a carbon nano tube, activated carbon, carbon nano fiber, graphene nano sheet or graphite oxide;
(3) according to the alkaline solution: the volume ratio of the mixed solution B is 1: slowly adding an alkali solution with a certain concentration into the mixed solution B according to a proportion of 50, and mixing and stirring for 10-30 minutes at room temperature to obtain a mixed solution C;
wherein: the alkali solution is KOH or NaOH or Na2CO3Or NaHCO3Or ammonia water with the concentration of 1 mol/L;
(4) performing solid-liquid separation on the mixed solution C obtained in the step (3), repeatedly washing with one or two washing solutions of deionized water and ethanol until the filtrate is neutral (namely the pH reaches 7), and freeze-drying the finally collected solid at-50 to-80 ℃ under the vacuum degree of 1-10 Pa for 4-24 hours to obtain a precursor of the carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material;
wherein: the solid-liquid separation is centrifugal separation or vacuum filtration, the rotating speed of the centrifugal separation is 2000-4000 r/min, and the vacuum degree of the vacuum filtration is-0.09 to-0.1 MPa;
(5) and (3) heating the precursor obtained in the step (4) to 300-600 ℃ in an inert gas, preserving the heat for 2-6 hours, and cooling to room temperature to obtain the carbon material in-situ deposited nano-lead crystal grain/lead oxide composite material.
Wherein: the inert gas is high-purity nitrogen or argon or helium;
after the technical scheme is adopted, the invention mainly has the following effects:
(1) the carbon material with low price, high conductivity and physical and chemical stability is used as a carrier, the nano lead crystal grains/lead oxide grow on the surface of the carbon material in situ, the combination mode of the carbon material and lead is structurally improved, the carbon material used as the carrier and the active substance used as lead are combined into a whole, the combination tightness of the lead crystal grains and the carbon material is improved to the greatest extent, the problem of uniform dispersity of the lead active substance in the carbon material carrier is fundamentally solved, the agglomeration phenomenon of the lead crystal grains and the lead oxide is restrained, favorable conditions are provided for the redox reaction of the lead active substance, the utilization rate of the lead active substance is effectively exerted, and the sulfation of a lead cathode is remarkably restrained;
(2) the method provided by the invention uniformly disperses the nano-lead crystal grains and the lead oxide on the surface of the carbon material, greatly improves the hydrogen evolution potential, the capacitance and the specific gravity of the carbon material, and has excellent electrochemical performance. The obtained composite material product is added into the negative electrode of the lead-carbon battery, so that the rate performance, the charge acceptance and the HRPSOC cycle life of the lead-carbon battery are obviously improved, and the water loss of the battery is reduced;
(3) the method adopts liquid phase reaction, centrifugation and simple chemical reaction to prepare the carbon material loaded lead/lead oxide composite material, has simple process, convenient operation, high production efficiency and small environmental burden, and is beneficial to large-scale production.
The method can be widely used for preparing the nano-lead crystal grain composite material, and the product prepared by the method can be widely applied to chemical power supplies such as lead-carbon batteries, lithium ion batteries, super capacitors and the like.
Drawings
Fig. 1 is an SEM electron microscope image of the carbon material in-situ deposited nano-lead crystal/lead oxide composite material prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following specific embodiments.
Example 1
The carbon material in-situ deposited nano lead/lead oxide grain composite material comprises the following components in percentage by mass:
carbon material 80%
15 percent of nano lead crystal grains
Lead oxide 5%
Wherein: the carbon material is a graphene nanosheet.
A method for preparing a carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material comprises the following specific steps:
(1) according to the mass (g) of the lead nitrate: volume (ml) ratio of deionized water 0.1: 500, dissolving lead nitrate into deionized water, and fully stirring to obtain a mixed solution A.
(2) Mass (g) of the carbon material: the volume ratio of the mixed solution A (ml) is 1:500, the carbon material was uniformly dispersed in the mixed solution a, and mixed and stirred at room temperature for 10 minutes to obtain a mixed solution B of the carbon material and a soluble lead salt.
Wherein: the carbon material is a graphene nanosheet.
(3) According to the alkaline solution: the volume ratio of the mixed solution B is 1: and (3) slowly adding an alkali solution with a certain concentration into the mixed solution B according to the proportion of 50, and mixing and stirring for 10 minutes at room temperature to obtain a mixed solution C.
Wherein: the alkali solution is NaOH.
(4) And (3) carrying out solid-liquid separation on the mixed solution C prepared in the step (3), repeatedly washing with one or two washing solutions of deionized water and ethanol until the filtrate is neutral (namely the pH reaches 7), and freeze-drying the finally collected solid at-50 ℃ under the vacuum degree of 10Pa for 12h to obtain the precursor of the carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material.
Wherein: the solid-liquid separation is centrifugal separation, and the rotating speed of the centrifugal separation is 3000 r/min.
(5) And (4) heating the precursor obtained in the step (4) to 300 ℃ in inert gas, preserving the heat for 6 hours, and cooling to room temperature to obtain the carbon material in-situ deposited nano lead crystal grain/lead oxide composite material.
Example 2
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 70%
24 percent of nano lead crystal grains
6 percent of lead oxide
Wherein: the carbon material is carbon nano-tube.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) ratio of 0.2: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: the ratio of the volume (mL) of the mixed solution a was 1:500, and stirring for 15 minutes. Wherein: the carbon material is carbon nano-tube.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, and stirring for 15 minutes. Wherein: the alkali solution is KOH solution.
In the step (4), the freeze-drying temperature is-60 ℃, the vacuum degree is 8Pa, and the freeze-drying time is 20. Wherein: the solid-liquid separation is vacuum filtration, and the vacuum degree is-0.095 MPa.
In the step (5), the heating temperature is 400 ℃, and the heat preservation time is 5 hours.
Example 3
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 60%
33 percent of nano lead crystal grains
Lead oxide 7%
Wherein: the carbon material is activated carbon.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.3: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 18 minutes. Wherein: the carbon material is activated carbon.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, stirring for 18 minutes. Wherein: the alkali solution is NaCO3And (3) solution.
In the step (4), the freeze-drying temperature is-70 ℃, the vacuum degree is 6Pa, and the freeze-drying time is 20 h. Wherein: the solid-liquid separation is centrifugal separation, and the rotating speed is 3800 r/min.
In the step (5), the heating temperature is 450 ℃, and the heat preservation time is 4 hours.
Example 4
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 50%
42 percent of nano lead crystal grains
Lead oxide 8%
Wherein: the carbon material is carbon nanofiber.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.4: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 20 minutes. Wherein: the carbon material is carbon nanofiber.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50The mixture was stirred for 22 minutes. Wherein: the alkali solution is NaHCO3And (3) solution.
In the step (4), the freeze-drying temperature is-78 ℃, the vacuum degree is 4Pa, and the freeze-drying time is 22 h. Wherein: the solid-liquid separation is vacuum filtration, and the vacuum degree is-0.096 MPa.
In the step (5), the heating temperature is 500 ℃, and the heat preservation time is 3 hours.
Example 5
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 40%
51 percent of nano lead crystal grains
9 percent of lead oxide
Wherein: the carbon material is graphite oxide.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.5: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 25 minutes. Wherein: the carbon material is graphite oxide.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, stirring for 28 minutes. Wherein: the alkali solution is NaOH solution.
In the step (4), the freeze-drying temperature is-80 ℃, the vacuum degree is 3Pa, and the freeze-drying time is 23 h. Wherein: the solid-liquid separation is centrifugal separation, and the rotating speed of the centrifugal separation is 4000 r/min.
In the step (5), the heating temperature is 550 ℃, and the heat preservation time is 2 hours.
Example 6
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 30%
60 percent of nano lead crystal grains
10 percent of lead oxide
Wherein: the carbon material is activated carbon.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.5: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 26 minutes. Wherein: the carbon material is carbon nanofiber.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, and stirring for 24 minutes. Wherein: the alkali solution is KOH solution.
In the step (4), the freeze-drying temperature is-76 ℃, the vacuum degree is 2Pa, and the freeze-drying time is 24 h. Wherein: the solid-liquid separation is vacuum filtration, and the vacuum degree is-0.097 MPa.
In the step (5), the heating temperature is 600 ℃, and the heat preservation time is 3 hours.
Example 7
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
20 percent of carbon material
75 percent of nano lead crystal grains
Lead oxide 5%
Wherein: the carbon material is carbon nanofiber.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.55: 500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 28 minutes. Wherein: the carbon material is carbon nanofiber.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, stirring for 28 minutes. Wherein: the alkali solution is KOH solution.
In the step (4), the freeze-drying temperature is-80 ℃, the vacuum degree is 2.5Pa, and the freeze-drying time is 24 h. Wherein: the solid-liquid separation is centrifugal separation, and the centrifugal rotating speed is 3700 r/min.
In the step (5), the heating temperature is 550 ℃, and the heat preservation time is 4 hours.
Example 8
The carbon material in-situ deposited nano lead crystal grain/lead oxide composite material comprises the following components in percentage by mass:
carbon material 10%
80 percent of nano lead crystal grains
10 percent of lead oxide
Wherein: the carbon material is a graphene nanosheet.
A method for preparing a carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, which is the same as in example 1, wherein:
in the step (1), the mixed solution A is prepared according to the mass (g) of lead nitrate: volume of deionized water (mL) 0.6:500 to the same scale.
In the step (2), the mixed solution B is prepared by mixing the carbon material: volume (mL) of mixed solution a was 1:500, and stirring for 30 minutes. Wherein: the carbon material is carbon nanofiber.
In the step (3), the mixed solution C is prepared according to the following alkali solution: the volume ratio of the mixed solution B is 1:50, and stirring for 30 minutes. Wherein: the alkali solution is NaOH solution.
In the step (4), the freeze-drying temperature is-80 ℃, the vacuum degree is 2Pa, and the freeze-drying time is 24 h. Wherein: the solid-liquid separation is vacuum filtration, and the vacuum degree is-0.01 MPa.
In the step (5), the heating temperature is 600 ℃, and the heat preservation time is 3 hours.
Test results
Scanning electron microscope characterization is performed on the carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material prepared in example 1, as shown in fig. 1.
As shown in figure 1, in the carbon material in-situ deposited nano lead crystal grain/lead oxide composite material, the grain size of the lead crystal grain/lead oxide is 10-500 nm, and the lead crystal grain/lead oxide is uniformly loaded on the surface and the interlayer of the carbon material, so that the agglomeration of lead particles is effectively prevented, and the carbon material also provides a smooth electron and heat transfer channel for the lead crystal grain and the nano lead oxide. The carbon material loaded with the nano lead crystal grains and the lead oxide can be well mixed with the lead active substance, so that the effective contact interfacial area of the lead active substance and the carbon material is increased, and the advantages of high conductivity and high capacitance of the carbon material are fully exerted. And the introduced lead has high hydrogen evolution overpotential, and when the composite material is added into the negative electrode of the lead-carbon battery, the problem of hydrogen evolution can be effectively inhibited in the later stage of charging, the charge and discharge performance is improved, and the cycle life of the battery is prolonged.
Claims (2)
1. The composite material of the carbon material in-situ deposited nano lead crystal grain/lead oxide is characterized by comprising the following components in percentage by mass:
10 to 80 percent of carbon material
80-15% of nano lead crystal grains
10 to 5 percent of lead oxide
Wherein: the carbon material is carbon nano tube or active carbon or carbon nano fiber or graphene nano sheet or graphite oxide, and the carbon content is at least more than 90%; the grain size of the nano lead crystal grains is 30-500 nm; the particle size of the lead oxide is 10-300 nm.
2. A method for preparing a carbon material in-situ deposited nano-lead crystal grain/lead oxide composite material is characterized by comprising the following steps:
(1) according to the mass of the soluble lead salt: the volume ratio of the deionized water is 0.1-0.6 g: dissolving soluble lead salt into deionized water according to the proportion of 500ml, and fully stirring to obtain a mixed solution A;
wherein: the soluble lead salt is lead nitrate or lead acetate or lead sulfate;
(2) according to the mass of the carbon material: the volume ratio of the mixed solution A is 1 g: uniformly dispersing the carbon material into the mixed solution A at a ratio of 500ml, and mixing and stirring at room temperature for 10-30 minutes to obtain a mixed solution B of the carbon material and soluble lead salt;
wherein: the carbon material is a carbon nano tube, activated carbon, carbon nano fiber, graphene nano sheet or graphite oxide;
(3) according to the mixed solution B: the volume ratio of the alkali solution is 1: slowly adding an alkali solution with a certain concentration into the mixed solution B according to a proportion of 50, and mixing and stirring for 10-30 minutes at room temperature to obtain a mixed solution C;
wherein: the alkali solution is KOH or NaOH or Na2CO3Or NaHCO3Or ammonia water with the concentration of 1 mol/L;
(4) carrying out solid-liquid separation on the mixed solution C obtained in the step (3), repeatedly washing with one or two washing solutions of deionized water and ethanol until the filtrate is neutral (namely the pH reaches 7), and drying the finally collected solid for 4-24 hours at-50 to-80 ℃ and under the vacuum degree of 1-10 Pa to obtain a precursor of the carbon material in-situ deposition nano lead crystal grain/lead oxide composite material;
wherein: the solid-liquid separation is centrifugal separation or vacuum filtration, the rotating speed of the centrifugal separation is 2000-4000 r/min, and the vacuum degree of the vacuum filtration is-0.09 to-0.1 MPa;
(5) and (3) heating the precursor obtained in the step (4) to 300-600 ℃ in an inert gas, preserving the heat for 2-6 hours, and cooling to room temperature to obtain the carbon material in-situ deposited nano-lead crystal grain/lead oxide composite material.
Wherein: the inert gas is high-purity nitrogen or argon or helium.
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| CN104505511A (en) * | 2014-11-20 | 2015-04-08 | 华中科技大学 | A lead-carbon composite material, a method for preparing the same, and applications thereof in a lead-carbon battery |
| CN106159258A (en) * | 2015-04-14 | 2016-11-23 | 郭永千 | The uniform mixing method of lead carbon battery nano-scale carbon |
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| CN103606656A (en) * | 2013-12-02 | 2014-02-26 | 华南师范大学 | Preparation method of lead oxide/graphene nanocomposite material for lead carbon super battery |
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