CN114759275A - Preparation method of lead-acid battery with graphene as additive - Google Patents

Preparation method of lead-acid battery with graphene as additive Download PDF

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Publication number
CN114759275A
CN114759275A CN202110495203.2A CN202110495203A CN114759275A CN 114759275 A CN114759275 A CN 114759275A CN 202110495203 A CN202110495203 A CN 202110495203A CN 114759275 A CN114759275 A CN 114759275A
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lead
graphene
parts
acid battery
positive
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CN114759275B (en
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吴嘉豪
李政文
黎少伟
肖笛青
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Guangzhou Zhuoyue Power Technology Co ltd
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Guangzhou Zhuoyue Power Technology Co ltd
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • 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
    • H01M10/12—Construction or manufacture
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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 discloses a preparation method of a lead-acid battery with graphene as an additive, wherein the lead-acid battery with graphene as the additive comprises a positive plate grid and a negative plate grid, positive lead plaster containing graphene is coated on the positive plate grid, negative lead plaster containing graphene is coated on the negative plate grid, and a preparation raw material of the negative lead plaster comprises a graphene intercalation lead sulfide composite material. The prepared lead-acid battery has long cycle service life and stability.

Description

Preparation method of lead-acid battery with graphene as additive
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to a preparation method of a lead-acid battery with graphene as an additive.
Background
The lead-acid storage battery is developed for more than one hundred years, has the advantages of mature technology, good safety performance, low cost, stable performance, high resource regeneration recovery rate and the like, and makes great contribution in many application aspects. However, the active materials in the lead-acid battery are not fully utilized, and the accumulation of the irreversible sulfation phenomenon can lead to the sharp reduction of the battery capacity.
Graphene (Graphene) is sp 2Carbon materials with hybrid-bonded carbon atoms densely packed in a single-layer two-dimensional honeycomb lattice structure have attracted worldwide attention for their excellent properties since their successful separation from graphite by physicists anderlic-gamm and costatin norvoschloff, manchester university, uk in 2004. Graphene has excellent conductivity, low resistance and huge specific surface area, and the excellent properties make it suitable for being used in lead-acid batteries. However, the uniform dispersion of graphene in the negative electrode has an important influence on the cycle number and stability of the battery.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a lead-acid battery using graphene as an additive, comprising the following steps:
s1, uniformly mixing an organic carbon source and organic sulfur, placing the mixture in a reflux tower, heating and refluxing while ultrasonically dispersing to prepare uniformly dispersed graphene reflux liquid; adding a lead salt solution into the graphene reflux liquid, then refluxing and stirring, simultaneously performing ultrasonic dispersion, filtering and washing after 3-5h to obtain a graphene intercalation lead sulfide composite material;
s2, uniformly mixing lead powder, the graphene intercalation lead sulfide composite material, the carbon nano tube, barium sulfate and polyester short fibers, adding water and sulfuric acid, and uniformly stirring to obtain lead-acid battery negative lead paste; coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene;
S3, uniformly mixing red lead, polyester short fibers, positive graphene, carbon fibers, conductive polymers and lead powder, adding water and sulfuric acid, and uniformly stirring to obtain lead paste of the positive electrode of the lead-acid battery; coating the positive lead plaster on a negative grid, and curing, drying and converting the positive lead plaster into a positive grid containing graphene;
s4, assembling the battery shell, the positive grid containing the graphene, the negative grid containing the graphene, electrolyte and the separator to obtain the lead-acid battery taking the graphene as the additive.
As a preferable technical scheme, in the S2, by weight, 80 to 100 parts of lead powder, 5 to 10 parts of graphene intercalation lead sulfide composite material, 1 to 3 parts of carbon nanotube, 1 to 3 parts of barium sulfate, 0.1 to 0.5 part of polyester staple fiber, 3 to 10 parts of sulfuric acid, and 5 to 15 parts of water.
As a preferable technical scheme, in the S3, by weight, 1-25 parts of red lead, 3-15 parts of sulfuric acid, 5-20 parts of water, 0.05-0.2 part of polyester short fiber, 0.5-1.5 parts of positive graphene, 0.1-0.5 part of conductive polymer and 40-60 parts of lead powder are added.
As a preferable technical scheme, the diameter of the polyester short fiber is less than 5 mm.
As a preferable technical scheme, the thickness of the positive electrode graphene is 1-5nm, and the sheet diameter is 1-3 μm.
As a preferred technical solution, the conductive polymer includes at least one of polypyrrole, polyacetylene, polythiophene, and polyaniline.
As a preferred technical scheme, the conductive polymer is a mixture of polypyrrole and polyaniline, and the weight ratio of the polypyrrole to the polyaniline is 1: (3-5).
As a preferred technical scheme, the weight ratio of the carbon nanotube to the graphene intercalated lead sulfide composite material is 1: (3-5).
As a preferred technical scheme, the diameter of the carbon nano tube is 5-20 nm.
As a preferable technical scheme, the specific surface area of the carbon nano tube is more than 220m2/g。
Has the advantages that:
in addition, the addition of the carbon nano tubes can also form a uniform conductive network with the graphene intercalation lead sulfide composite material on the negative electrode, and the cycle number and the stability of the battery are greatly influenced.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
As used herein, a feature that is not limited to a single plural form is also intended to include plural forms of the feature unless the context clearly indicates otherwise. It will also be understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "containing," and/or "containing," when used in this specification denotes a stated composition, step, method, article, or apparatus, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or apparatuses. Furthermore, the use of "preferred," "preferably," "more preferred," and the like, when describing embodiments of the present invention, is intended to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above problems, the present invention provides a lead-acid battery with graphene as an additive, including a positive grid and a negative grid, wherein the positive grid is coated with a positive lead plaster containing graphene, and the negative grid is coated with a negative lead plaster containing graphene.
In some preferred embodiments, the raw materials for preparing the positive electrode lead paste comprise, by weight, 1-25 parts of red lead, 3-15 parts of sulfuric acid, 5-20 parts of water, 0.05-0.2 part of polyester short fibers, 0.5-1.5 parts of graphene, 0.1-0.5 part of conductive polymers and 40-60 parts of lead powder.
In some preferred embodiments, the polyester staple fibers have a diameter of less than 5 mm.
In some preferred embodiments, the graphene has a thickness of 1 to 5nm and a sheet diameter of 1 to 3 μm.
In some preferred embodiments, the conductive polymer includes at least one of polypyrrole, polyacetylene, polythiophene, polyaniline.
In some preferred embodiments, the conductive polymer is a mixture of polypyrrole and polyaniline, and the weight ratio is 1: (3-5).
The preparation method of the positive lead paste comprises the following steps:
1) uniformly mixing red lead, polyester staple fibers, graphene, carbon fibers, conductive polymers and lead powder to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery positive electrode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
In some preferred embodiments, the raw material for preparing the negative lead paste comprises a graphene intercalated lead sulfide composite material. The preparation method of the graphene intercalated lead sulfide composite material comprises the following steps:
s1, uniformly mixing an organic carbon source and organic sulfur, placing the mixture in a reflux tower, heating and refluxing the mixture, and performing ultrasonic dispersion on the mixture at the same time to prepare uniformly dispersed graphene reflux liquid;
s2, adding a lead salt solution into the graphene reflux liquid, then refluxing and stirring, performing ultrasonic dispersion simultaneously, filtering and washing after 3-5 hours to obtain the lead sulfide-graphene composite electrode material.
In some preferred embodiments, the raw materials for preparing the negative lead plaster comprise 80-100 parts of lead powder, 5-10 parts of graphene intercalation lead sulfide composite material, 1-3 parts of carbon nano tube, 1-3 parts of barium sulfate, 0.1-0.5 part of polyester short fiber, 3-10 parts of sulfuric acid and 5-15 parts of water.
In some preferred embodiments, the raw materials for preparing the negative lead paste further include carbon nanotubes, and the weight ratio of the carbon nanotubes to the graphene intercalated lead sulfide composite material is 1: (3-5).
In some preferred embodiments, the carbon nanotubes have a diameter of 5 to 20nm and a specific surface area of more than 220m2/g。
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
The invention also provides a preparation method of the lead-acid battery with the graphene as the additive, which comprises the following steps: assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
The present invention will be specifically described below by way of examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention described above will now occur to those skilled in the art.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples.
Example 1
Embodiment 1 provides a method for preparing a lead-acid battery using graphene as an additive, where the lead-acid battery includes a positive grid and a negative grid, the positive grid is coated with a positive lead paste containing graphene, and the negative grid is coated with a negative lead paste containing graphene.
The raw materials for preparing the positive lead plaster comprise, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene, 0.3 part of conductive polymer and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The graphene is 1-5nm in thickness and 1-3 μm in sheet diameter, and is purchased from Jiangsu Xifeng nanometer material science and technology Limited company, and the model is XF 022-17440-44-0.
The conductive polymer is a mixture of polypyrrole (purchased from Hubei Yunmagnesi science and technology Co., Ltd.) and polyacetylene (Hubei Xin Rundy chemical Co., Ltd.), and the weight ratio is 1: 4.
The preparation method of the positive lead paste comprises the following steps:
1) mixing the red lead, the polyester short fibers, the graphene, the carbon fibers, the conductive polymer and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery positive electrode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster comprises 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and simultaneously performing ultrasonic dispersion at the power of 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to the organic sulfur in the S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000 watts of power, filtering and washing after 4 hours to obtain the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Darkland island technologies, Inc. of Beijing.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Example 2
Embodiment 2 provides a method for preparing a lead-acid battery with graphene as an additive, where the lead-acid battery includes a positive grid and a negative grid, the positive grid is coated with a positive lead paste containing graphene, and the negative grid is coated with a negative lead paste containing graphene.
The raw materials for preparing the positive lead plaster comprise, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene, 0.3 part of conductive polymer and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The graphene is 1-5nm in thickness and 1-3 μm in sheet diameter, and is purchased from Jiangsu Xifeng nanometer material science and technology Limited company, and the model is XF 022-17440-44-0.
The conductive polymer is a mixture of polypyrrole (purchased from Hubei Yunmagnesi science and technology Co., Ltd.) and polyacetylene (Hubei Xin Rundy chemical Co., Ltd.), and the weight ratio is 1: 4.
the preparation method of the positive lead paste comprises the following steps:
1) mixing the red lead, the polyester short fibers, the graphene, the carbon fibers, the conductive polymer and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery anode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster is prepared from 90 parts of lead powder, 6 parts of graphene intercalation lead sulfide composite material, 3 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to organic sulfur in S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000W, filtering and washing after 4h, and obtaining the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Darkland island technologies, Inc. of Beijing.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) Uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Example 3
Embodiment 3 provides a method for preparing a lead-acid battery using graphene as an additive, where the lead-acid battery includes a positive grid and a negative grid, the positive grid is coated with a positive lead paste containing graphene, and the negative grid is coated with a negative lead paste containing graphene.
The raw materials for preparing the positive lead plaster comprise, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fibers, 0.5 part of graphene, 0.3 part of conductive polymers and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The thickness of the graphene is 1-5nm, the sheet diameter is 1-3 mu m, and the graphene is purchased from Jiangsu Xiancheng nano material science and technology limited company, and the model is XF 022-17440-44-0.
The conductive polymer is a mixture of polypyrrole (purchased from Hubei Yunw science and technology Co., Ltd.) and polyacetylene (Hubei Xin Rundy chemical Co., Ltd.), and the weight ratio is 1: 4.
the preparation method of the positive lead paste comprises the following steps:
1) uniformly mixing red lead, polyester staple fibers, graphene, carbon fibers, conductive polymers and lead powder according to the formula ratio to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery positive electrode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster comprises 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to organic sulfur in S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000W, filtering and washing after 4h, and obtaining the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Darkland island technologies, Inc. of Beijing.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) Mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Example 4
Embodiment 4 provides a method for preparing a lead-acid battery using graphene as an additive, where the lead-acid battery includes a positive grid and a negative grid, the positive grid is coated with a positive lead paste containing graphene, and the negative grid is coated with a negative lead paste containing graphene.
The positive pole lead plaster comprises, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene, 0.2 part of conductive polymer and 50 parts of lead powder.
The polyester staple fibers have an average diameter of 1.5mm, are available from Hangzhou Moss mechanical fibers, Inc., have a product number of 6202 and a specification of 1.5D 32.
The graphene is 1-5nm in thickness and 1-3 μm in sheet diameter, and is purchased from Jiangsu Xifeng nanometer material science and technology Limited company, and the model is XF 022-17440-44-0.
The conductive polymer is a mixture of polypyrrole (purchased from Hubei Yunmagnesi science and technology Co., Ltd.) and polyacetylene (Hubei Xin Rundy chemical Co., Ltd.), and the weight ratio is 1: 4.
the preparation method of the positive lead paste comprises the following steps:
1) mixing the red lead, the polyester short fibers, the graphene, the carbon fibers, the conductive polymer and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery positive electrode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster comprises 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
S1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to the organic sulfur in the S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000 watts of power, filtering and washing after 4 hours to obtain the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Daidaku island technologies, Inc., Beijing.
The polyester staple fibers have an average diameter of 1.5mm, are available from Hangzhou Moss mechanical fibers, Inc., have a product number of 6202 and a specification of 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) Adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Example 5
Embodiment 5 provides a method for preparing a lead-acid battery using graphene as an additive, where the lead-acid battery includes a positive grid and a negative grid, the positive grid is coated with a positive lead paste containing graphene, and the negative grid is coated with a negative lead paste containing graphene.
The raw materials for preparing the positive lead plaster comprise, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene, 0.3 part of conductive polymer and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The graphene is 1-5nm in thickness and 1-3 μm in sheet diameter, and is purchased from Jiangsu Xifeng nanometer material science and technology Limited company, and the model is XF 022-17440-44-0.
The conductive polymer is polypyrrole, and is purchased from Hubei cloud magnesium technology Co., Ltd.
The preparation method of the positive lead paste comprises the following steps:
1) mixing the red lead, the polyester short fibers, the graphene, the carbon fibers, the conductive polymer and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery anode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster is prepared from 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
S2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to organic sulfur in S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000W, filtering and washing after 4h, and obtaining the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Darkland island technologies, Inc. of Beijing.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Comparative example 1
Comparative example 1 provides a method for preparing a lead-acid battery with graphene as an additive, the lead-acid battery including a positive grid coated with positive lead plaster containing graphene and a negative grid coated with negative lead plaster containing graphene.
The positive pole lead plaster comprises, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene, 0.3 part of conductive polymer and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The thickness of the graphene is 1-5nm, the sheet diameter is 1-3 mu m, and the graphene is purchased from Jiangsu Xiancheng nano material science and technology limited company, and the model is XF 022-17440-44-0.
The conductive polymer is a mixture of polypyrrole (purchased from Hubei Yunw science and technology Co., Ltd.) and polyacetylene (Hubei Xin Rundy chemical Co., Ltd.), and the weight ratio is 1: 4.
the preparation method of the positive lead paste comprises the following steps:
1) Mixing the red lead, the polyester short fibers, the graphene, the carbon fibers, the conductive polymer and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery anode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster is prepared from 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to organic sulfur in S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000W, filtering and washing after 4h, and obtaining the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(g) from King of Deke island, BeijingTechnology limited, model CNT 103.
The polyester staple fibers have an average diameter of 1.5mm, are available from Hangzhou Moss mechanical fibers, Inc., have a product number of 6202 and a specification of 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Comparative example 2
The comparative example 2 provides a preparation method of a lead-acid battery with graphene as an additive, and the lead-acid battery comprises a positive grid and a negative grid, wherein the positive grid is coated with positive lead plaster containing graphene, and the negative grid is coated with negative lead plaster containing graphene.
The raw materials for preparing the positive lead plaster comprise, by weight, 10 parts of red lead, 8 parts of sulfuric acid, 12 parts of water, 0.1 part of polyester staple fiber, 1 part of graphene and 50 parts of lead powder.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The graphene is 1-5nm in thickness and 1-3 μm in sheet diameter, and is purchased from Jiangsu Xifeng nanometer material science and technology Limited company, and the model is XF 022-17440-44-0.
The preparation method of the positive lead paste comprises the following steps:
1) mixing the red lead, the polyester short fiber, the graphene, the carbon fiber and the lead powder uniformly according to the formula amount to obtain a mixed material for later use;
2) mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery anode lead paste.
And coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain the positive grid containing graphene.
The negative lead plaster is prepared from 90 parts of lead powder, 8 parts of graphene intercalation lead sulfide composite material, 2 parts of carbon nano tube, 2 parts of barium sulfate, 0.3 part of polyester short fiber, 5 parts of sulfuric acid and 10 parts of water.
The graphene intercalation lead sulfide composite material comprises the following steps:
s1, uniformly mixing 2 parts of glucose and 8 parts of thiourea according to a molar ratio, placing the mixture in a reflux tower, heating and refluxing for 2 hours at 200 ℃, and performing ultrasonic dispersion at 2000 watts to prepare uniformly dispersed graphene reflux liquid;
s2, adding a 20% lead acetate solution into the graphene reflux liquid, wherein the molar ratio of the content of lead acetate in the added lead acetate solution to organic sulfur in S1 is 1.3: 1. and then refluxing and stirring at 120 ℃, performing ultrasonic dispersion at 2000W, filtering and washing after 4h, and obtaining the lead sulfide-graphene composite electrode material.
The diameter of the carbon nano tube is 8-15nm, and the specific surface area is more than 233m2(ii)/g, model CNT103, available from Darkland island technologies, Inc. of Beijing.
The average diameter of the polyester staple fiber is 1.5mm, the polyester staple fiber is purchased from Hangzhou Moss mechanical fiber, Inc., the product number is 6202, and the specification is 1.5D 32.
The preparation method of the negative electrode lead paste comprises the following steps:
1) uniformly mixing lead powder, a graphene intercalation lead sulfide composite material, a carbon nano tube, barium sulfate and polyester short fibers to obtain a mixed material for later use;
2) Mixing half of water and sulfuric acid uniformly to obtain a mixed solution for later use;
3) adding the mixed solution while stirring the mixed materials, adding the rest water after the mixed solution is completely added, and uniformly stirring to obtain the lead-acid battery cathode lead paste.
And coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene.
Assembling a battery shell, a positive grid containing graphene, a negative grid containing graphene, electrolyte and a separator to obtain the lead-acid battery taking the graphene as an additive.
Evaluation of Performance
Lead-acid batteries of 12V and 12A were produced according to the above examples and comparative examples.
1. Service life test
Testing the cycle times of the prepared lead-acid storage battery, recording that the lead-acid storage battery is qualified when the cycle times are higher than 700 times, and otherwise, recording that the lead-acid storage battery is unqualified; the test results are shown in Table 1.
2. Stability test
And (3) detecting the discharge time of the prepared lead-acid storage battery when the lead-acid storage battery is cycled for 300 times, if the discharge time is higher than 150min, recording that the lead-acid storage battery is qualified, otherwise, recording that the lead-acid storage battery is unqualified, and obtaining a test result shown in table 1.
TABLE 1
Figure BDA0003054105000000151
Figure BDA0003054105000000161
According to the embodiment and the comparative example, the invention provides the preparation method of the lead-acid battery with the graphene as the additive, and the prepared lead-acid battery has long cycle service life and stability.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a lead-acid battery with graphene as an additive is characterized by comprising the following steps:
s1, uniformly mixing an organic carbon source and organic sulfur, placing the mixture in a reflux tower, heating and refluxing while ultrasonically dispersing to prepare uniformly dispersed graphene reflux liquid; adding a lead salt solution into the graphene reflux liquid, then refluxing and stirring, simultaneously performing ultrasonic dispersion, filtering and washing after 3-5h to obtain a graphene intercalation lead sulfide composite material;
s2, uniformly mixing lead powder, the graphene intercalation lead sulfide composite material, the carbon nano tube, barium sulfate and polyester short fibers, adding water and sulfuric acid, and uniformly stirring to obtain lead-acid battery negative lead paste; coating the negative lead plaster on a negative grid, and curing, drying and converting to obtain the negative grid containing graphene;
s3, uniformly mixing red lead, polyester short fibers, positive graphene, carbon fibers, conductive polymers and lead powder, adding water and sulfuric acid, and uniformly stirring to obtain lead paste of the positive electrode of the lead-acid battery; coating the positive lead plaster on a negative grid, and curing, drying and converting to obtain a positive grid containing graphene;
S4, assembling the battery shell, the positive grid containing the graphene, the negative grid containing the graphene, electrolyte and the separator to obtain the lead-acid battery taking the graphene as the additive.
2. The method for preparing a lead-acid battery with graphene as an additive according to claim 1, is characterized in that: in the S2, by weight, 80-100 parts of lead powder, 5-10 parts of graphene intercalation lead sulfide composite material, 1-3 parts of carbon nano tube, 1-3 parts of barium sulfate, 0.1-0.5 part of polyester short fiber, 3-10 parts of sulfuric acid and 5-15 parts of water.
3. The method for preparing a lead-acid battery with graphene as an additive according to claim 1, is characterized in that: in the S3, by weight, 1-25 parts of red lead, 3-15 parts of sulfuric acid, 5-20 parts of water, 0.05-0.2 part of polyester staple fiber, 0.5-1.5 parts of positive graphene, 0.1-0.5 part of conductive polymer and 40-60 parts of lead powder are used.
4. The method for preparing a lead-acid battery with graphene as an additive according to any one of claims 2 or 3, wherein the graphene is prepared by the following steps: the diameter of the polyester staple fiber is less than 5 mm.
5. The method for preparing a lead-acid battery with graphene as an additive according to claim 3, is characterized in that: the thickness of the positive electrode graphene is 1-5nm, and the sheet diameter is 1-3 mu m.
6. The method for preparing a lead-acid battery with graphene as an additive according to claim 3, is characterized in that: the conductive polymer comprises at least one of polypyrrole, polyacetylene, polythiophene and polyaniline.
7. The method for preparing a lead-acid battery with graphene as an additive according to claim 6, is characterized in that: the conductive polymer is a mixture of polypyrrole and polyaniline, and the weight ratio of the polypyrrole to the polyaniline is 1: (3-5).
8. The method for preparing a lead-acid battery with graphene as an additive according to claim 2, is characterized in that: the weight ratio of the carbon nano tube to the graphene intercalation lead sulfide composite material is 1: (3-5).
9. The method for preparing a lead-acid battery with graphene as an additive according to claim 8, is characterized in that: the diameter of the carbon nano tube is 5-20 nm.
10. Graphene according to claim 9The preparation method of the lead-acid battery as the additive is characterized by comprising the following steps: the specific surface area of the carbon nano tube is more than 220m2/g。
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