CN110620212A - Lead storage battery electrode plate based on carbon gelatinized lignin and preparation method thereof - Google Patents

Lead storage battery electrode plate based on carbon gelatinized lignin and preparation method thereof Download PDF

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Publication number
CN110620212A
CN110620212A CN201910895858.1A CN201910895858A CN110620212A CN 110620212 A CN110620212 A CN 110620212A CN 201910895858 A CN201910895858 A CN 201910895858A CN 110620212 A CN110620212 A CN 110620212A
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parts
carbon
lignin
gelatinized
lead
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张正东
伊晓波
林思略
方腾云
陈卫东
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QUANZHOU KAIYING POWER SUPPLY ELECTRICAL APPLIANCES CO Ltd
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QUANZHOU KAIYING POWER SUPPLY ELECTRICAL APPLIANCES 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H01M4/21—Drying of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/624—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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lead storage battery polar plate based on carbon gelatinized lignin and a preparation method thereof, wherein the lead storage battery polar plate comprises a lead alloy plate body, and composite material lead plaster is coated on the surface of the lead alloy plate body; the composite lead plaster is prepared from the following raw materials in parts by weight: 78-85 parts of lead powder, 12-15 parts of carboxymethyl cellulose, deionized water, 6-9 parts of sulfuric acid and 5-8 parts of carbon gelatinized lignin; the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 3-5 parts of fumed nano silicon dioxide, 2.5-3.5 parts of graphene, 3-4.5 parts of semi-carbon lignin, 10-12 parts of deionized water, 5.1-5.6 parts of acetone, 7.5-8.8 parts of sulfuric acid, 0.4-0.7 part of barium hydroxide, 0.18-0.23 part of aluminum silicate, 0.25-0.35 part of nano barium sulfate and 0.03-0.05 part of polyacrylamide. The lead storage battery polar plate is used for manufacturing a lead storage battery, and has the characteristics of large capacity, strong heavy current discharge capacity and long cycle life compared with the traditional lead storage battery.

Description

Lead storage battery electrode plate based on carbon gelatinized lignin and preparation method thereof
Technical Field
The invention relates to the field of electrochemical power sources, in particular to a lead storage battery polar plate based on carbon gelatinized lignin and a preparation method thereof.
Background
The battery manufacturing industry is an important component of both the traditional industry and the new energy industry in China, is closely associated with a plurality of strategic emerging industries such as new energy automobiles, renewable energy sources, modern electronic information, new materials and equipment manufacturing, has wide application fields and very important functions in the aspects of guaranteeing the strategic needs of national defense, meeting the demands of mass work and diversified living consumption and the like.
In the world, excessive consumption of fossil fuels and the environmental problems caused by the excessive consumption become key factors for restricting the development of human society, and the establishment of novel high-efficiency energy-saving and low-carbon societies becomes a hot spot of global attention. In which, the development of new energy vehicles is vigorously carried out, and the reduction of petroleum consumption and environmental pollution brought by fuel vehicles has become the key point of transformation and upgrading of the global automobile industry. Since 2016 northern european countries announced that the sale of conventional fuel automobiles was stopped by 2030, developed countries such as europe, the united states, japan, and the like, including asian countries of china, gradually announced the direction and schedule of the development of automobiles to be motorized and intelligent.
The semi-carbon lignin is a natural organic material integrating the effects of carbon and lignin. The addition of a separate carbon material to the battery plate lead paste material may serve to increase conductivity and inhibit the formation of irreversible lead sulfate. The single lignin added into the negative plate of the storage battery can play a role in refining the crystal grain structure of the active substance, increasing the surface energy of the active substance, improving the low-temperature starting capability of the battery and prolonging the service life. However, the hydrophobicity and the freeness of the carbon material and the lignin are defects, and have a limiting side effect on ensuring high capacity and long service life of the storage battery. The semi-carbon lignin is a composite material of a carbon material and lignin, and high stability and strong hydrophilicity of the composite particles are realized by improving particle structures of the carbon material and the lignin on the basis of keeping the effects of the carbon material and the lignin. The carbon gelatinized lignin is applied to the lead-acid storage battery, has the characteristics of good high-rate discharge performance, high charging acceptance capacity, long service life and the like, is suitable for the application of low-speed electric automobiles, automobile start-stop systems and energy storage systems, and becomes the best choice for the application and popularization of the low-speed electric automobiles.
However, the lead-acid batteries currently used have the following problems: the transformation and upgrading products are urgently needed, the capacity and the large-current discharge capacity of the lead storage battery are improved, the service life of the lead storage battery is prolonged, and the like.
Disclosure of Invention
Based on the above situation, the present invention aims to provide a lead storage battery plate based on carbon gelatinized lignin and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body, wherein the surface of the lead alloy plate body is coated with composite material lead plaster; the composite lead plaster is prepared from the following raw materials in parts by weight:
78-85 parts of lead powder, 1.3-1.6 parts of carboxymethyl cellulose, 12-15 parts of deionized water, 6-9 parts of sulfuric acid and 5-8 parts of carbon gelatinized lignin;
the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 3-5 parts of fumed nano silicon dioxide, 2.5-3.5 parts of graphene, 3-4.5 parts of semi-carbon lignin, 10-12 parts of deionized water, 5.1-5.6 parts of acetone, 7.5-8.8 parts of sulfuric acid, 0.4-0.7 part of barium hydroxide, 0.18-0.23 part of aluminum silicate, 0.25-0.35 part of nano barium sulfate and 0.03-0.05 part of polyacrylamide;
wherein the gas-phase-method nano-silica is a gas-phase-method nano-silica which is originally produced by Wacker chemical Co., Ltd, Germany and has the model number of N20;
the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 32-36%;
wherein the mass fraction of carbon element in the semi-carbon lignin is (44 +/-1)%, the mass fraction of hydrogen element is (6 +/-0.4)%, and the mass fraction of oxygen element is (42.5 +/-1)%; and the mass fraction of mineral ash in the semi-carbon lignin is (1 +/-0.1)%.
Preferably, the composite lead plaster is prepared from the following raw materials in parts by weight: 82 parts of lead powder, 1.45 parts of carboxymethyl cellulose, 13.5 parts of deionized water, 7.6 parts of sulfuric acid and 6.8 parts of carbon-gelatinized lignin.
Preferably, the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 4.2 parts of gas phase method nano silicon dioxide, 3 parts of graphene, 3.7 parts of semi-carbon lignin, 10.8 parts of deionized water, 5.4 parts of acetone, 8.3 parts of sulfuric acid, 0.55 part of barium hydroxide, 0.21 part of aluminum silicate, 0.29 part of nano barium sulfate and 0.04 part of polyacrylamide.
Preferably, the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 34.6%.
Preferably, the partial graphene oxide is multilayer partial graphene oxide, and the number of layers is 8-12.
Preferably, the mass fraction of carbon element in the semi-carbon lignin is 44%, the mass fraction of hydrogen element is 6.4%, and the mass fraction of oxygen element is 42.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 1%.
Preferably, the average particle size of the nano barium sulfate is 180-220 nm.
Preferably, H in the sulfuric acid2SO4The mass fraction of (A) is 38.5-42.5%.
Preferably, the preparation method of the carbogelling lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultrahigh-speed dispersion, shearing and emulsification for 4-6 min at a rotation speed of 5000-6000 r/min;
C. slowly adding sulfuric acid, stirring and mixing at the rotating speed of 1500-2000 r/min, and continuously stirring for 30-40 min in the whole process;
D. then adding gas phase method nano silicon dioxide, and adopting the rotation speed of 5000-6000 r/min to carry out 60-70 min ultrahigh speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing ultrahigh-speed emulsification and dispersion for 30-40 min at the rotating speed of 5000-6000 r/min; then, under the condition that the temperature is 48-55 ℃, the mixture is emulsified and dispersed at a high speed in 15-20 min at a rotating speed of 3000-4000 r/min, and acetone is volatilized; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
The invention also provides a preparation method of the lead storage battery plate based on the carbon gelatinized lignin, which comprises the following steps:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotating speed of 2000-2500 r/min, and continuously stirring for 60-90 min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at the rotating speed of 2000-2500 r/min at the temperature of 40-45 ℃, and continuously stirring for 30-40 min in the whole process to prepare the composite material lead plaster;
4) and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the lead-acid storage battery polar plate based on the carbon gelatinized lignin is used for manufacturing a lead-acid storage battery, and compared with the traditional lead-acid storage battery, the manufactured lead-acid storage battery has the characteristics of large capacity, strong heavy current discharge capacity and long cycle life, and can be widely applied to auxiliary power supplies of electric passenger vehicles, plug-in hybrid electric vehicles, electric logistics vehicles, low-speed electric four-wheel vehicles and the like.
The carbon gelatinized lignin adopted in the lead storage battery polar plate based on the carbon gelatinized lignin is a novel composite material prepared from graphene, nano silica gel, semi-carbon lignin and the like, and when the composite material is applied to the lead storage battery, the porosity of an active substance of the polar plate is improved, the surface energy of the active substance is increased, and meanwhile, the technical difficulties that the battery capacity, large-current discharge and cycle life are influenced due to large electrolyte permeability and electrode concentration polarization in the electrochemical reaction process of the battery at present are effectively solved.
The semi-carbon lignin (semi-carbon lignin) adopted in the lead storage battery polar plate based on the carbon gelatinized lignin is a natural organic material integrating the effects of carbon and lignin. The addition of a separate carbon material to the battery plate lead paste material may serve to increase conductivity and inhibit the formation of irreversible lead sulfate. The single lignin added into the negative plate of the storage battery can play a role in refining the crystal grain structure of the active substance, increasing the surface energy of the active substance, improving the low-temperature starting capability of the battery and prolonging the service life. However, the hydrophobicity and the freeness of the carbon material and the lignin are defects, and have a limiting side effect on ensuring high capacity and long service life of the storage battery. The semi-carbon lignin is a composite material of a carbon material and lignin, and high stability and strong hydrophilicity of the composite particles are realized by improving particle structures of the carbon material and the lignin on the basis of keeping the effects of the carbon material and the lignin.
The carbon gelatinized lignin disclosed by the invention is applied to lead-acid storage batteries, has the characteristics of good high-rate discharge performance, high charging acceptance capacity, long service life and the like, is suitable for low-speed electric automobiles, automobile start-stop systems and energy storage systems, and has a wide popularization prospect in the application of low-speed electric automobiles.
The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
a lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body, wherein the surface of the lead alloy plate body is coated with composite material lead plaster; the composite lead plaster is prepared from the following raw materials in parts by weight:
78-85 parts of lead powder, 1.3-1.6 parts of carboxymethyl cellulose, 12-15 parts of deionized water, 6-9 parts of sulfuric acid and 5-8 parts of carbon gelatinized lignin;
the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 3-5 parts of fumed nano silicon dioxide, 2.5-3.5 parts of graphene, 3-4.5 parts of semi-carbon lignin, 10-12 parts of deionized water, 5.1-5.6 parts of acetone, 7.5-8.8 parts of sulfuric acid, 0.4-0.7 part of barium hydroxide, 0.18-0.23 part of aluminum silicate, 0.25-0.35 part of nano barium sulfate and 0.03-0.05 part of polyacrylamide;
wherein the gas-phase-method nano-silica is a gas-phase-method nano-silica which is originally produced by Wacker chemical Co., Ltd, Germany and has the model number of N20;
the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 32-36%;
wherein the mass fraction of carbon element in the semi-carbon lignin is (44 +/-1)%, the mass fraction of hydrogen element is (6 +/-0.4)%, and the mass fraction of oxygen element is (42.5 +/-1)%; and the mass fraction of mineral ash in the semi-carbon lignin is (1 +/-0.1)%.
Preferably, the composite lead plaster is prepared from the following raw materials in parts by weight: 82 parts of lead powder, 1.45 parts of carboxymethyl cellulose, 13.5 parts of deionized water, 7.6 parts of sulfuric acid and 6.8 parts of carbon-gelatinized lignin.
Preferably, the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 4.2 parts of gas phase method nano silicon dioxide, 3 parts of graphene, 3.7 parts of semi-carbon lignin, 10.8 parts of deionized water, 5.4 parts of acetone, 8.3 parts of sulfuric acid, 0.55 part of barium hydroxide, 0.21 part of aluminum silicate, 0.29 part of nano barium sulfate and 0.04 part of polyacrylamide.
Preferably, the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 34.6%.
Preferably, the partial graphene oxide is multilayer partial graphene oxide, and the number of layers is 8-12.
Preferably, the mass fraction of carbon element in the semi-carbon lignin is 44%, the mass fraction of hydrogen element is 6.4%, and the mass fraction of oxygen element is 42.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 1%.
Preferably, the average particle size of the nano barium sulfate is 180-220 nm.
Preferably, H in the sulfuric acid2SO4The mass fraction of (A) is 38.5-42.5%.
Preferably, the preparation method of the carbogelling lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultrahigh-speed dispersion, shearing and emulsification for 4-6 min at a rotation speed of 5000-6000 r/min;
C. slowly adding sulfuric acid, stirring and mixing at the rotating speed of 1500-2000 r/min, and continuously stirring for 30-40 min in the whole process;
D. then adding gas phase method nano silicon dioxide, and adopting the rotation speed of 5000-6000 r/min to carry out 60-70 min ultrahigh speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing ultrahigh-speed emulsification and dispersion for 30-40 min at the rotating speed of 5000-6000 r/min; then, under the condition that the temperature is 48-55 ℃, the mixture is emulsified and dispersed at a high speed in 15-20 min at a rotating speed of 3000-4000 r/min, and acetone is volatilized; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
The embodiment also provides a preparation method of the lead storage battery plate based on the carbon gelatinized lignin, which comprises the following steps:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotating speed of 2000-2500 r/min, and continuously stirring for 60-90 min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at the rotating speed of 2000-2500 r/min at the temperature of 40-45 ℃, and continuously stirring for 30-40 min in the whole process to prepare the composite material lead plaster;
4) and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
Example 2:
a lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body, wherein the surface of the lead alloy plate body is coated with composite material lead plaster; the composite lead plaster is prepared from the following raw materials in parts by weight:
78 parts of lead powder, 1.3 parts of carboxymethyl cellulose, 12 parts of deionized water, 6 parts of sulfuric acid and 5 parts of carbon gelatinized lignin;
the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 3 parts of gas phase method nano silicon dioxide, 2.5 parts of graphene, 3 parts of semi-carbon lignin, 10 parts of deionized water, 5.1 parts of acetone, 7.5 parts of sulfuric acid, 0.4 part of barium hydroxide, 0.18 part of aluminum silicate, 0.25 part of nano barium sulfate and 0.03 part of polyacrylamide;
wherein the gas-phase-method nano-silica is a gas-phase-method nano-silica which is originally produced by Wacker chemical Co., Ltd, Germany and has the model number of N20;
the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 32%;
wherein the mass fraction of carbon element in the semi-carbon lignin is 43%, the mass fraction of hydrogen element is 6.4%, and the mass fraction of oxygen element is 43.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 0.9%.
In this embodiment, the partial graphene oxide is a multilayer partial graphene oxide, and the number of layers is 8.
In this example, the average particle size of the nano barium sulfate was 180 nm.
In this example, H in the sulfuric acid2SO4Is 38.5 percent.
In this embodiment, the preparation method of the gelatinized lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultra-high speed dispersion, shearing and emulsification for 6min at a rotation speed of 5000 r/min;
C. slowly adding sulfuric acid, stirring and mixing at a rotation speed of 1500r/min, and continuously stirring for 40min in the whole process;
D. then adding gas phase method nanometer silicon dioxide, adopting the rotation speed of 5000r/min to carry out 70min ultra-high speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing ultra-high speed emulsification dispersion for 40min at the rotating speed of 5000 r/min; then emulsifying and dispersing at a high speed for 20min at a rotating speed of 3000r/min under the condition that the temperature is 48 ℃, and volatilizing the acetone; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
The embodiment also provides a preparation method of the lead storage battery plate based on the carbon gelatinized lignin, which comprises the following steps:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotating speed of 2000r/min, and continuously stirring for 90min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at a rotation speed of 2000r/min at 40 ℃, and continuously stirring for 40min in the whole process to prepare the composite material lead plaster;
4) and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
Example 3:
a lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body, wherein the surface of the lead alloy plate body is coated with composite material lead plaster; the composite lead plaster is prepared from the following raw materials in parts by weight:
85 parts of lead powder, 1.6 parts of carboxymethyl cellulose, 15 parts of deionized water, 9 parts of sulfuric acid and 8 parts of carbon gelatinized lignin;
the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 5 parts of gas phase method nano silicon dioxide, 3.5 parts of graphene, 4.5 parts of semi-carbon lignin, 12 parts of deionized water, 5.6 parts of acetone, 8.8 parts of sulfuric acid, 0.7 part of barium hydroxide, 0.23 part of aluminum silicate, 0.35 part of nano barium sulfate and 0.05 part of polyacrylamide;
wherein the gas-phase-method nano-silica is a gas-phase-method nano-silica which is originally produced by Wacker chemical Co., Ltd, Germany and has the model number of N20;
the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 36%;
wherein the mass fraction of carbon element in the semi-carbon lignin is 45%, the mass fraction of hydrogen element is 5.6%, and the mass fraction of oxygen element is 41.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 1.1%.
In this embodiment, the partial graphene oxide is a multilayer partial graphene oxide, and the number of layers is 12.
In this example, the average particle size of the nano barium sulfate was 220 nm.
In this example, H in the sulfuric acid2SO4The mass fraction of (a) is 42.5%.
In this embodiment, the preparation method of the gelatinized lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultrahigh-speed dispersion, shearing and emulsification for 4min at a rotating speed of 6000 r/min;
C. slowly adding sulfuric acid, stirring and mixing at a rotation speed of 2000r/min, and continuously stirring for 30min in the whole process;
D. then adding gas phase method nanometer silicon dioxide, adopting the rotation speed of 6000r/min to carry out 60min ultra-high speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing 30min ultrahigh-speed emulsification dispersion again at the rotating speed of 6000 r/min; then emulsifying and dispersing at a high speed for 15min at a rotation speed of 4000r/min under the condition that the temperature is 55 ℃, and volatilizing the acetone; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
The embodiment also provides a preparation method of the lead storage battery plate based on the carbon gelatinized lignin, which comprises the following steps:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotating speed of 2500r/min, and continuously stirring for 60min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at a rotation speed of 2500r/min at the temperature of 45 ℃, and continuously stirring for 30min in the whole process to prepare the composite material lead plaster;
4) and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
Example 4:
a lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body, wherein the surface of the lead alloy plate body is coated with composite material lead plaster; the composite lead plaster is prepared from the following raw materials in parts by weight:
82 parts of lead powder, 1.45 parts of carboxymethyl cellulose, 13.5 parts of deionized water, 7.6 parts of sulfuric acid and 6.8 parts of carbon-gelatinized lignin.
In this embodiment, the gelatinized lignin is prepared from the following raw materials in parts by weight: 4.2 parts of gas phase method nano silicon dioxide, 3 parts of graphene, 3.7 parts of semi-carbon lignin, 10.8 parts of deionized water, 5.4 parts of acetone, 8.3 parts of sulfuric acid, 0.55 part of barium hydroxide, 0.21 part of aluminum silicate, 0.29 part of nano barium sulfate and 0.04 part of polyacrylamide.
In this embodiment, the graphene is partially oxidized graphene, and the relative content of hydroxyl groups and carboxyl groups in the partially oxidized graphene is 34.6%.
In this embodiment, the partial graphene oxide is a multilayer partial graphene oxide, and the number of layers is 10.
In the embodiment, the mass fraction of carbon element in the semi-carbon lignin is 44%, the mass fraction of hydrogen element is 6.4%, and the mass fraction of oxygen element is 42.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 1%.
In this example, the average particle size of the nano barium sulfate was 200 nm.
In this example, H in the sulfuric acid2SO4The mass fraction of (a) is 40.6%.
In this embodiment, the preparation method of the gelatinized lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultrahigh-speed dispersion, shearing and emulsification for 5min at a rotation speed of 5500 r/min;
C. slowly adding sulfuric acid, stirring and mixing at a rotation speed of 1800r/min, and continuously stirring for 35min in the whole process;
D. then adding gas phase method nanometer silicon dioxide, adopting rotation speed of 5500r/min to carry out 65min ultra-high speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing 35min ultrahigh-speed emulsification dispersion again at a rotation speed of 5500 r/min; then emulsifying and dispersing at high speed in 18min at the rotation speed of 3500r/min at the temperature of 52 ℃ and volatilizing acetone; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
The embodiment also provides a preparation method of the lead storage battery plate based on the carbon gelatinized lignin, which comprises the following steps:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotation speed of 2250r/min, and continuously stirring for 75min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at a rotation speed of 2250r/min at 42 deg.C for 35min to obtain composite lead paste;
4) and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
The following performance tests are performed on the lead-acid battery plates based on carbon gelatinized lignin obtained in embodiments 2 to 4 of the present invention, specifically, the lead-acid battery plates based on carbon gelatinized lignin obtained in embodiments 2 to 4 of the present invention are respectively made into lead-acid batteries by referring to the prior art (chinese patent application No. CN 201310322763.3), and the performance tests are performed, and the test results are shown in tables 1 and 2:
TABLE 1
TABLE 2
Low temperature discharge voltage of 30s Circulate 120 times Circulate 240 times Circulating 360 times
Example 2 8.52 7.85 7.26
Example 3 8.61 7.93 7.32
Example 4 8.72 8.01 7.39
GB/T5008.1-2013 ≥7.2 — —
From the above table 2, it can be seen that when the carbon gelatinized lignin-based lead storage battery plate of the invention is used for manufacturing a lead-acid storage battery, the voltage of low-temperature discharge for 30s is obviously higher than 7.2V when the discharge cycle is 120 times, the cycle durability is better, the service life of the lead storage battery is greatly prolonged, and when the discharge cycle is 240 times and 360 times, the voltage of low-temperature discharge for 30s is still higher than 7.2V, which indicates that the lead-acid storage battery manufactured by the carbon gelatinized lignin-based lead storage battery plate of the invention has long service life.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Claims (10)

1. A lead storage battery polar plate based on carbon gelatinized lignin comprises a lead alloy plate body and is characterized in that composite material lead plaster is coated on the surface of the lead alloy plate body; the composite lead plaster is prepared from the following raw materials in parts by weight:
78-85 parts of lead powder, 1.3-1.6 parts of carboxymethyl cellulose, 12-15 parts of deionized water, 6-9 parts of sulfuric acid and 5-8 parts of carbon gelatinized lignin;
the carbon gelatinized lignin is prepared from the following raw materials in parts by weight: 3-5 parts of fumed nano silicon dioxide, 2.5-3.5 parts of graphene, 3-4.5 parts of semi-carbon lignin, 10-12 parts of deionized water, 5.1-5.6 parts of acetone, 7.5-8.8 parts of sulfuric acid, 0.4-0.7 part of barium hydroxide, 0.18-0.23 part of aluminum silicate, 0.25-0.35 part of nano barium sulfate and 0.03-0.05 part of polyacrylamide;
wherein the gas-phase-method nano-silica is a gas-phase-method nano-silica which is originally produced by Wacker chemical Co., Ltd, Germany and has the model number of N20;
the graphene is partially oxidized graphene, and the relative content of hydroxyl and carboxyl in the partially oxidized graphene is 32-36%;
wherein the mass fraction of carbon element in the semi-carbon lignin is (44 +/-1)%, the mass fraction of hydrogen element is (6 +/-0.4)%, and the mass fraction of oxygen element is (42.5 +/-1)%; and the mass fraction of mineral ash in the semi-carbon lignin is (1 +/-0.1)%.
2. The carbon-gelatinized lignin-based lead-acid battery plate according to claim 1, wherein the composite lead paste is prepared from the following raw materials in parts by weight: 82 parts of lead powder, 1.45 parts of carboxymethyl cellulose, 13.5 parts of deionized water, 7.6 parts of sulfuric acid and 6.8 parts of carbon-gelatinized lignin.
3. The carbon-gelatinized lignin-based lead-acid battery plate according to claim 1, wherein the carbon-gelatinized lignin is prepared from the following raw materials in parts by weight: 4.2 parts of gas phase method nano silicon dioxide, 3 parts of graphene, 3.7 parts of semi-carbon lignin, 10.8 parts of deionized water, 5.4 parts of acetone, 8.3 parts of sulfuric acid, 0.55 part of barium hydroxide, 0.21 part of aluminum silicate, 0.29 part of nano barium sulfate and 0.04 part of polyacrylamide.
4. The carbon-gelled-lignin-based lead-acid battery plate according to claim 3, wherein the graphene is partially oxidized graphene, and the relative content of hydroxyl groups and carboxyl groups in the partially oxidized graphene is 34.6%.
5. The carbon-gelatinized lignin-based lead-acid battery plate according to claim 4, wherein the partial graphene oxide is a plurality of layers of partial graphene oxide, and the number of the layers is 8-12.
6. The carbon-gelatinized lignin-based lead-acid battery plate according to claim 3, wherein the mass fraction of carbon element in the semi-char lignin is 44%, the mass fraction of hydrogen element is 6.4%, and the mass fraction of oxygen element is 42.5%; and the mass fraction of mineral ash in the semi-carbon lignin is 1%.
7. The carbon-gelatinized lignin-based lead-acid battery plate according to claim 1, wherein the average particle size of the nano barium sulfate is 180 to 220 nm.
8. The carbon-gelatinized lignin-based lead acid battery plate according to claim 1, wherein H in sulfuric acid is2SO4The mass fraction of (A) is 38.5-42.5%.
9. The carbon-gelatinized lignin-based lead storage battery plate according to claim 1, wherein the preparation method of the carbon-gelatinized lignin comprises the following steps:
A. weighing the following components in parts by weight: gas-phase method nanometer silicon dioxide, graphene, semi-carbon lignin, deionized water, acetone, sulfuric acid, barium hydroxide, aluminum silicate, nanometer barium sulfate and polyacrylamide;
B. mixing deionized water, acetone, graphene, semi-carbon lignin, barium hydroxide, aluminum silicate and nano barium sulfate, and performing ultrahigh-speed dispersion, shearing and emulsification for 4-6 min at a rotation speed of 5000-6000 r/min;
C. slowly adding sulfuric acid, stirring and mixing at the rotating speed of 1500-2000 r/min, and continuously stirring for 30-40 min in the whole process;
D. then adding gas phase method nano silicon dioxide, and adopting the rotation speed of 5000-6000 r/min to carry out 60-70 min ultrahigh speed emulsification dispersion;
E. finally, adding polyacrylamide, and performing ultrahigh-speed emulsification and dispersion for 30-40 min at the rotating speed of 5000-6000 r/min; then, under the condition that the temperature is 48-55 ℃, the mixture is emulsified and dispersed at a high speed in 15-20 min at a rotating speed of 3000-4000 r/min, and acetone is volatilized; stopping emulsification and dispersion to obtain the carbon gelatinized lignin.
10. A method for the preparation of a carbon-gelled lignin based lead-acid battery plate according to any one of claims 1 to 9, comprising the steps of:
1) weighing the following components in parts by weight: lead powder, carboxymethyl cellulose, deionized water, sulfuric acid and carbon gelatinized lignin;
2) mixing lead powder, carboxymethyl cellulose, deionized water and carbon gelatinized lignin, stirring and mixing at the rotating speed of 2000-2500 r/min, and continuously stirring for 60-90 min in the whole process;
3) slowly adding sulfuric acid, stirring and mixing at the rotating speed of 2000-2500 r/min at the temperature of 40-45 ℃, and continuously stirring for 30-40 min in the whole process to prepare the composite material lead plaster;
and then coating the composite material lead plaster on a negative plate, and drying and curing to obtain the lead storage battery plate based on the carbon gelatinized lignin.
CN201910895858.1A 2019-09-21 2019-09-21 Lead storage battery electrode plate based on carbon gelatinized lignin and preparation method thereof Pending CN110620212A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1588685A (en) * 2004-09-27 2005-03-02 扬州华富实业有限公司 Process for preparing silicon mixed colloid electrolyte of lead acid accumulator
CN105977485A (en) * 2016-07-07 2016-09-28 无锡市宝来电池有限公司 Lead paste of lead acid storage battery with long service cycle
CN106207279A (en) * 2016-08-24 2016-12-07 宁波中科孚奇能源科技有限公司 A kind of preparation method of lead crystalline substance carbon accumulator

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1588685A (en) * 2004-09-27 2005-03-02 扬州华富实业有限公司 Process for preparing silicon mixed colloid electrolyte of lead acid accumulator
CN105977485A (en) * 2016-07-07 2016-09-28 无锡市宝来电池有限公司 Lead paste of lead acid storage battery with long service cycle
CN106207279A (en) * 2016-08-24 2016-12-07 宁波中科孚奇能源科技有限公司 A kind of preparation method of lead crystalline substance carbon accumulator

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Application publication date: 20191227