CN115188961A - Lead-carbon battery negative lead paste, preparation method, battery pole plate, preparation method and application - Google Patents
Lead-carbon battery negative lead paste, preparation method, battery pole plate, preparation method and application Download PDFInfo
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- CN115188961A CN115188961A CN202210791820.1A CN202210791820A CN115188961A CN 115188961 A CN115188961 A CN 115188961A CN 202210791820 A CN202210791820 A CN 202210791820A CN 115188961 A CN115188961 A CN 115188961A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 93
- 229920000642 polymer Polymers 0.000 claims abstract description 74
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000002002 slurry Substances 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 32
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 239000011505 plaster Substances 0.000 claims abstract description 25
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004021 humic acid Substances 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 10
- 229920000767 polyaniline Polymers 0.000 claims abstract description 4
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 52
- 239000003999 initiator Substances 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 15
- 239000002019 doping agent Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229920005550 ammonium lignosulfonate Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 7
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 239000003365 glass fiber Substances 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 102220043159 rs587780996 Human genes 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000002427 irreversible effect Effects 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 230000019635 sulfation Effects 0.000 description 5
- 238000005670 sulfation reaction Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- 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 application discloses a lead-carbon battery negative electrode lead plaster, a preparation method, a battery plate, a preparation method and an application, wherein the lead-carbon battery negative electrode lead plaster comprises the following raw materials in parts by weight: 100 parts of lead powder; 5-10 parts of graphene-based polymer; 0.5-1.0 part of barium sulfate; 0.05 to 0.5 portion of humic acid; 0.05 to 0.3 portion of short fiber; 0.01-0.5 parts of conductive carbon black; 0.1-5 parts of water; the graphene-based polymer is prepared by doping at least one of polypyrrole and polyaniline with lignosulfonate and taking graphene as a skeleton. The invention provides graphene-based polymer slurry lead-carbon negative electrode lead paste and a preparation method thereof. The graphene-based polymer composite material is applied to the traditional lead-acid storage battery, and due to the introduction of the graphene-based polymer composite material, the cycle life of the high-rate part charge of the battery is prolonged.
Description
Technical Field
The application relates to the technical field of battery materials and preparation thereof, in particular to a lead-carbon battery negative electrode lead paste, a preparation method, a battery polar plate, a preparation method and application, and belongs to the field of lead-acid batteries or lead-carbon battery additives.
Background
Lead-acid batteries, which have been on the market for over 150 years, still hold a significant position in chemical power sources, and account for about half of the market. At present, most of electric vehicles adopt lead-acid batteries as power batteries because of low cost, rich raw material resources and easy availability. In addition, the service temperature range of the battery is wide, the failed battery can be recycled, the resource utilization rate is high, the environmental pollution is low, and most importantly, the safety performance is high. With the continuous development of new energy storage and new energy power markets, particularly in hybrid electric vehicles and intermittent new energy storage applications, the secondary battery is required to have good charge acceptance and long cycle life in a high-power partial charge state. However, the conventional lead-acid battery cannot meet the requirement, and the main reason is that ions and electrons cannot react due to irreversible coarse sulfation formed on the negative plate, so that the deterioration of the plate is further aggravated. In order to improve the phenomenon, a high-carbon-content carbon material is added into the negative electrode to prepare the negative electrode with high carbon content required by the lead-carbon battery, and the method has the advantages that the introduction of the carbon material improves the conductivity and the capacitance of the negative electrode, greatly limits the coarseness of lead sulfate and inhibits the irreversible sulfation of the negative electrode. However, the graphene has a very high specific surface area, a very large difference from the density of lead powder, and a great difficulty in dispersion, and the strength of the negative plate is also reduced once the content is increased.
Disclosure of Invention
Based on the above problems, the present application provides a graphene-based polymer composite lead-carbon negative electrode lead paste and a preparation method thereof. The lead plaster is applied to the traditional lead-acid battery, and the introduction of the graphene-based polymer composite material can reduce the formation of irreversible coarse sulfate on a negative plate, reduce the internal resistance of the battery, improve the utilization rate of active substances, improve the strength of the negative plate, finally realize the improvement of the charging acceptance of the battery and slow down the sulfation of the negative plate, thereby prolonging the cycle life of the high-rate part of the charge of the battery. The lead paste has the same effect when being used for a lead-carbon battery or a super battery.
Polypyrrole and polyaniline are doped by lignosulfonate, graphene is used as a framework, graphene-based polymer slurry is prepared, and then the graphene-based polymer slurry is applied to lead-acid negative electrode lead paste to prepare a high-performance lead-carbon battery. Due to the introduction of the graphene-based polymer composite material, the irreversible coarse sulfate formed by the negative plate can be reduced, the internal resistance of the battery is reduced, the utilization rate of active substances is improved, the strength of the negative plate can be improved, the charging acceptance of the battery is finally improved, the sulfation of the negative electrode is slowed down, and therefore the cycle life of the high-rate part of the charge of the battery is prolonged.
In one aspect of the application, the lead-carbon battery negative electrode lead paste comprises the following raw materials in parts by weight:
100 parts of lead powder;
5-10 parts of graphene-based polymer;
0.5-1.0 part of barium sulfate;
0.05 to 0.5 portion of humic acid;
0.05 to 0.3 portion of short fiber;
0.01-0.5 parts of conductive carbon black;
0.1-5 parts of water;
the graphene-based polymer is prepared by doping at least one of polypyrrole and polyaniline with lignosulfonate, taking graphene as a framework and doping an adhesive thickener.
Optionally, the parts by weight of the graphene-based polymer are independently selected from any of 5, 8, and 10 or any value between any two of the foregoing.
Optionally, the parts by weight of the barium sulfate are independently selected from any of 0.5, 0.8, 1.0 or any value between any two of the foregoing.
Optionally, the parts by weight of humic acid are independently selected from any of 0.05, 0.1, 0.3, 0.5 or any value between any two of the foregoing.
Optionally, the weight fraction of the staple fibers is independently selected from any of 0.05, 0.1, 0.2, 0.3 or any value between any two of the foregoing.
Optionally, the weight parts of the conductive carbon black are independently selected from any of 0.01, 0.25, 0.5 or any value between any two of the foregoing.
Optionally, the parts by weight of water are independently selected from any of 0.1, 0.2, 0.5, 0.8, 1.0, 1.5, 2.0, 3.0, 5.0 parts or any value between any two of the foregoing.
Optionally, the particle size D50 of the graphene is less than or equal to 2 μm;
optionally, the particle size D50 of the graphene is 0.5 μm to 2 μm;
optionally, the particle size D50 of the graphene is independently selected from any value of 0.5 μm, 0.8 μm, 1.0 μm, 2 μm, or any value between any two of the foregoing.
Optionally, the lignosulfonate is selected from at least one of ammonium lignosulfonate, potassium lignosulfonate, sodium lignosulfonate;
the bonding thickener is at least one selected from sodium carboxymethylcellulose and styrene butadiene rubber.
In another aspect of the present application, there is provided a method for preparing the lead paste for the negative electrode of the lead-carbon battery, where the raw material of the lead paste includes graphene-based polymer slurry;
optionally, the preparation method comprises:
mixing raw materials I containing lead powder, barium sulfate, humic acid, short fibers and conductive carbon black according to the proportion to obtain a premixed material; and mixing II the slurry containing the graphene-based polymer with the premixed material and water to obtain the lead-carbon battery negative electrode lead paste.
Optionally, the preparation method of the graphene-based polymer-containing slurry includes:
mixing a water-based precursor solution containing a polymer monomer, graphene, sulfuric acid, a sulfonate dopant and an adhesive thickener with an initiator solution, and preparing the slurry containing the graphene-based polymer by adopting a chemical oxidation method.
Optionally, in the precursor solution, the weight parts of each component are as follows:
100 parts of water;
60-120 parts of sulfuric acid;
10-20 parts of graphene;
1-5 parts of polymer monomer;
0.3-1.5 parts of sulfonate dopant;
0.1 to 1.0 portion of adhesive thickening agent.
Optionally, the weight parts of the sulfuric acid are independently selected from any of 60, 80, 100, and 120 or any value between any two of the foregoing.
Optionally, the parts by weight of the graphene are independently selected from any value of 10, 15, and 20 or any value between any two points.
Optionally, the parts by weight of the polymer monomer are independently selected from any of 1, 2, 3, 4, 5 or any value between any two of the foregoing.
Optionally, the weight fraction of the sulfonate dopant is independently selected from any of 0.3, 0.5, 0.8, 1.0, 1.2, 1.5, or any value between any two of the foregoing.
Optionally, the parts by weight of the binding thickener are independently selected from any of 0.1, 0.3, 0.5, 0.8, 1.0, or any value between any two of the foregoing.
Optionally, the precursor solution is obtained under stirring conditions; adopting a high-speed shearing and stirring mode;
the stirring speed is 1200 r/min-1500 r/min; stirring for 60min or more, mainly dispersing the solution uniformly.
Optionally, the stirring rate is independently selected from any of 1200r/min, 1300r/min, 1400r/min, 1500r/min or any value between any of the above.
Optionally, the polymer monomer is selected from at least one of pyrrole and aniline;
the sulfonate dopant is selected from at least one of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate;
the bonding thickener is at least one of sodium carboxymethylcellulose and styrene butadiene rubber;
optionally, the concentration of sulfuric acid is 36wt.%.
Optionally, the initiator solution comprises the following components in parts by weight:
80-90 parts of water;
10-20 parts of initiator.
Optionally, the parts by weight of the water are independently selected from any of 80, 85, and 90 or any value between any two of the foregoing.
Optionally, the weight fraction of the initiator is independently selected from any of 10, 15, and 20 or any value between any two of the foregoing.
Optionally, the initiator is selected from at least one of ammonium persulfate, sodium persulfate, potassium persulfate, and hydrogen peroxide;
optionally, the weight ratio of the initiator solution to the precursor solution is 1:5-1; the initiator solution is slowly added to the precursor solution.
Optionally, the weight ratio of the initiator solution to the precursor solution is independently selected from 1: 5. 1: 6. 1: 7. 1: 8. 1: 9. 1:10 or any value between any two of the above points.
Optionally, the initiator solution is added to the precursor solution at a dropping rate of 15ml/min to 25 ml/min.
Optionally, the dropping rate is independently selected from any of 15ml/min, 20ml/min, 25ml/min, or any value between any two of the above.
Optionally, the preparation method of the premix material comprises:
(1) Mixing raw materials containing lead powder, barium sulfate, sodium sulfate and humic acid to form a mixture I;
(2) Adding short fibers into the mixture I to form a mixture II;
(3) Adding a carbon material to the mixture II to obtain the premix material.
Optionally, the mixing II comprises:
stirring the slurry containing the graphene-based polymer and the premixed material, mixing the slurry and the premixed material, adding water to adjust the mixture, and enabling the apparent density of the lead plaster to reach 4.0-4.6 g/cm 3 And then the paste is obtained.
Optionally, the apparent density of the lead paste is independently selected from 4.0g/cm 3 、4.1g/cm 3 、4.2g/cm 3 、4.31g/cm 3 、4.48g/cm 3 、4.52g/cm 3 、4.6g/cm 3 Or any value between any two points described above.
Optionally, the temperature of the paste is generally within 60 ℃.
As a specific embodiment, the preparation method comprises the following steps:
a) Preparing graphene-based polymer slurry;
b) Premixing raw material components except the graphene-based polymer slurry to prepare a premixed material;
c) And stirring and pasting the graphene-based polymer slurry and the premixed material to obtain paste, thus obtaining the lead-carbon negative electrode lead paste of the graphene-based polymer slurry.
In the step A), the method for preparing the graphene-based polymer slurry comprises the steps of adding an initiator solution into a water-based precursor solution containing a polymer monomer, graphene, sulfuric acid, a sulfonate dopant and an adhesive thickener in a certain proportion, and preparing the graphene-based polymer slurry by adopting a chemical oxidation method.
The initiator solution is prepared from water and an initiator;
wherein, in the step B), the premixed material comprises lead powder, barium sulfate, humic acid, short fibers and carbon materials; the preparation process of the premixed material needs to add and mix in a certain sequence, and the lead powder, the barium sulfate, the sodium sulfate and the humic acid are required to be added and mixed firstly, then the short fibers are added and mixed, and finally the carbon material is added and mixed.
Wherein, in the step C), the graphene-based polymer slurry and the premixed material are stirred and pasted, water is added for regulation, and the apparent density of the lead paste reaches 4.0-4.6 g/cm 3 And (4) obtaining the graphene-based polymer slurry lead-carbon negative electrode lead paste after the paste is obtained according to the requirements.
In yet another aspect of the present application, a battery plate is provided, the battery plate including lead paste;
the lead plaster is at least one selected from the lead-carbon battery negative electrode lead plaster or the lead-carbon battery negative electrode lead plaster prepared by the preparation method;
optionally, the battery plate is a battery negative plate.
Optionally, the preparation method comprises:
and coating the lead plaster on a grid, and curing to obtain the battery plate.
Optionally, the grid is selected from at least one of a lead-tin-calcium grid and a continuous rolling continuous pressing alloy lead grid.
Optionally, the curing comprises a first stage curing and a second stage curing;
wherein, the process conditions of the first stage curing are as follows: curing for 24-48 h under the atmosphere conditions of 50-80 ℃ and 80-100% of humidity.
Optionally, the temperature of the first stage curing is independently selected from any of 50 ℃,60 ℃, 70 ℃,80 ℃ or any value between any two of the foregoing.
Optionally, the atmosphere humidity of the first stage curing is independently selected from any value of 80%, 90%, 100% or any value between any two of the above.
Optionally, the first stage curing time is independently selected from any of 24h, 32h, 40h, 48h or any value between any two of the above.
Optionally, the process conditions of the second stage curing are as follows: curing for 5-30 min at 100-120 deg.c.
Optionally, the temperature of the second stage curing is independently selected from any of 100 ℃, 105 ℃, 110 ℃, 115 ℃,120 ℃ or any value between any two of the foregoing.
Optionally, the time of the second stage curing is independently selected from any value of 5min, 10min, 15min, 20min, 25min, 30min or any value between any two of the above.
In a further aspect of the present application, there is provided a use of the battery plate or the battery plate prepared by the above preparation method in a battery, wherein the battery includes at least one selected from a lead-acid battery, a lead-carbon battery and a lead-carbon battery.
Optionally, the lead-acid or lead-carbon battery comprises a negative battery plate;
the battery negative plate is obtained by coating the lead plaster on a grid and curing.
Optionally, the method of making the battery (preferably a lead-acid battery) comprises: assembling a lead-acid battery core according to the arrangement sequence of the positive plate, the glass fiber, the negative plate, the glass fiber and the positive plate, injecting sulfuric acid electrolyte, and sealing a battery shell to prepare the battery (the lead-acid battery).
The beneficial effects that this application can produce include:
the invention provides graphene-based polymer slurry lead-carbon negative electrode lead paste and a preparation method thereof. The graphene-based polymer composite material is applied to the traditional lead-acid storage battery, and due to the introduction of the graphene-based polymer composite material, the irreversible coarse sulfate formed on the negative plate can be reduced, the internal resistance of the battery is reduced, the utilization rate of active substances is improved, the strength of the negative plate can be improved, the charging acceptance of the battery is finally improved, and the sulfation of the negative plate is slowed down, so that the cycle life of the high-rate part charge of the battery is prolonged. The lead paste has the same effect when being used for a lead-carbon battery or a super battery.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Example 1
Preparation of lead plaster
Step 1 preparation of graphene-based polymer slurry
The graphene-based polymer slurry was prepared by a chemical oxidation method by adding an initiator solution to an aqueous precursor solution containing a polymer monomer, graphene (particle size D50=2.0 μm), sulfuric acid, a sulfonate dopant, and a binding thickener.
Wherein, the precursor solution contains 100 parts of water by weight; 100 parts of sulfuric acid (36% by mass); 20 parts of graphene; 4 parts of pyrrole; 1.2 parts of sodium lignosulfonate; 0.5 part of sodium carboxymethyl cellulose; and in the process of preparing the precursor solution, dispersing in a high-speed shearing and stirring mode at 1200r/min (the stirring time is not less than 60min until the dispersion is uniform).
The initiator solution is prepared from water and ammonium persulfate, and comprises the following components in parts by weight: 90 parts of water; ammonium persulfate, 15 parts.
The weight ratio of the initiator solution to the precursor solution is 1:9; the initiator solution was slowly added to the precursor solution using 20 ml/min.
Step 2 preparation of negative lead plaster
Graphene-based polymer slurry
The preparation method of the negative electrode lead paste comprises the following steps:
(1) Premixing other raw material components except the graphene-based polymer slurry (without special requirements, mechanically and physically mixing uniformly) to prepare a premixed material; the other raw materials include lead powder, barium sulfate, humic acid, and polyester staple fiber (diameter)
Micron) and conductive carbon black; the preparation process of the premixed material needs to add and mix according to a certain sequence, and the lead powder, the barium sulfate, the sodium sulfate and the humic acid are required to be added and mixed firstly, then the polyester short fiber is added and mixed, and finally the conductive carbon black is added and mixed.
(2) Stirring and pasting the graphene-based polymer slurry prepared in the step (1) and the premixed material (the temperature of the paste is controlled within 60 ℃), adding water for regulation during stirring and pasting, and enabling the apparent density of the lead paste to reach 4.48g/cm 3 And (3) discharging paste to obtain the graphene-based polymer slurry lead-carbon negative electrode lead paste, wherein the raw materials are in parts by mass: 100 parts of lead powder; 5 parts of graphene-based polymer slurry; 0.5 part of barium sulfate; 0.1 part of humic acid; 0.05 part of polyester staple fiber; 0.5 part of conductive carbon black; 0.1-5 parts of water (the specific dosage of the water is based on the lead plaster apparent density).
EXAMPLE 2 preparation of Battery plates
And (3) coating the lead plaster prepared in the embodiment 1 on a lead-tin-calcium grid, and curing to obtain a battery plate.
The curing comprises two stages of curing, namely, the first stage of low-temperature high-humidity curing and the second stage of high-temperature curing. The first stage is as follows: curing for 48h under the atmosphere conditions of the temperature of 60 ℃ and the humidity of 90 percent. And a second stage: curing at 105 deg.C for 10min.
EXAMPLE 3 preparation of lead-acid Battery
A lead-acid battery cell is assembled by using a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, a negative plate (a battery plate prepared in example 2), the glass fibers and the positive plate, and 1.265g/cm of lead-acid battery cell is injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
EXAMPLE 4 preparation of lead paste
Step 1 preparation of graphene-based polymer slurry
The graphene-based polymer slurry was prepared by a chemical oxidation method by adding an initiator solution to an aqueous precursor solution containing a polymer monomer, graphene (particle size D50=1.0 μm), sulfuric acid, a sulfonate dopant, and a binding thickener.
Wherein, the precursor solution contains 100 parts of water by weight; 120 parts of sulfuric acid; 15 parts of graphene; 5 parts of aniline; 1.0 part of sodium lignosulfonate; 0.8 part of styrene butadiene rubber. And in the process of preparing the precursor solution, dispersing in a high-speed shearing and stirring mode of 1500r/min (the stirring time is not less than 60min until the dispersion is uniform).
The initiator solution is prepared from water and ammonium persulfate, and comprises the following components in parts by weight: 80 parts of water; ammonium persulfate, 20 parts.
The weight ratio of the initiator solution to the precursor solution is 1:5; the initiator solution was slowly added to the precursor solution using 25 ml/min.
Step 2 preparation of negative lead plaster
The preparation method of the graphene-based polymer slurry lead-carbon negative electrode lead paste comprises the following steps:
(1) Removing the graphene-based polymer slurryOther raw material components are pre-mixed (no special requirement is needed, and the raw material components are mechanically and physically mixed uniformly) to prepare a pre-mixed material; the other raw materials include lead powder, barium sulfate, humic acid, and polyester staple fiber (diameter)
Micron) and conductive carbon black; the preparation process of the premixed material needs to add and mix in a certain sequence, and the lead powder, the barium sulfate, the sodium sulfate and the humic acid are required to be added and mixed firstly, then the polyester short fiber is added and mixed, and finally the conductive carbon black is added and mixed.
(2) Stirring and pasting the graphene-based polymer slurry prepared in the step (1) and the premixed material (the temperature of the paste is controlled within 60 ℃), adding water for regulation when stirring and pasting, and enabling the apparent density of the lead paste to reach 4.31g/cm 3 And (3) discharging paste to obtain the graphene-based polymer slurry lead-carbon negative electrode lead paste, wherein the raw materials are in parts by mass: 100 parts of lead powder; 10 parts of graphene-based polymer slurry; 0.8 part of barium sulfate; 0.3 part of humic acid; 0.1 part of polyester staple fiber; 0.25 part of conductive carbon black; 0.1-5 parts of water (the specific dosage of the water is based on the lead plaster apparent density).
EXAMPLE 5 preparation of Battery plates
And coating the lead paste prepared in the example 4 on a lead-tin-calcium grid, and curing to obtain a battery plate.
The curing comprises two stages of curing, namely, the first stage of low-temperature high-humidity curing and the second stage of high-temperature curing. The first stage is as follows: curing for 48 hours under the atmosphere conditions of 60 ℃ and 90% humidity. And a second stage: curing at 105 deg.C for 10min.
EXAMPLE 6 preparation of lead-acid Battery
A lead-acid battery cell is assembled by using a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, a negative plate (a battery plate prepared in example 5), the glass fibers and the positive plate, and 1.265g/cm of the positive plate, the glass fibers and the conductive agent are injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
EXAMPLE 7 preparation of lead paste
Step 1 preparation of graphene-based polymer slurry
The graphene-based polymer slurry was prepared by a chemical oxidation method by adding an initiator solution to an aqueous precursor solution containing a polymer monomer, graphene (particle size D50=0.8 μm), sulfuric acid, a sulfonate dopant, and a binding thickener.
Wherein, the precursor solution contains 100 parts of water by weight; 100 parts of sulfuric acid; 20 parts of graphene; 4 parts of pyrrole; 1.2 parts of sodium lignosulfonate; 0.5 part of sodium carboxymethyl cellulose and 0.5 part of styrene-butadiene rubber (the mass ratio is 6:4). And in the process of preparing the precursor solution, dispersing in a high-speed shearing and stirring mode of 1500r/min (the stirring time is not less than 60min until the dispersion is uniform).
The initiator solution is prepared from water and ammonium persulfate, and comprises the following components in parts by weight: 90 parts of water; ammonium persulfate, 15 parts.
The weight ratio of the initiator solution to the precursor solution is 1:9; the initiator solution was slowly added to the precursor solution using 15 ml/min.
Step 2 preparation of negative lead plaster
The preparation method of the graphene-based polymer slurry lead-carbon negative electrode lead paste comprises the following steps:
(1) Premixing other raw material components except the graphene-based polymer slurry (without special requirements, mechanically and physically mixing uniformly) to prepare a premixed material; the other raw materials include lead powder, barium sulfate, humic acid, and polyester staple fiber (diameter)
Micron) and conductive carbon black; the preparation process of the premixed material needs to add and mix in a certain sequence, and requires that lead powder, barium sulfate, sodium sulfate and humic acid are added and mixed firstly, then short fibers are added and mixed, and finally carbon material conductive carbon black is added and mixed.
(2) Stirring and pasting the graphene-based polymer slurry prepared in the step (1) and the premixed material (the temperature of the pasted material is controlled within 60 ℃), adding water for regulation during stirring and pasting, and leadingThe apparent density of the lead paste reaches 4.52g/cm 3 And (3) obtaining the graphene-based polymer slurry lead-carbon negative electrode lead paste by obtaining the paste according to the following raw materials in parts by mass: 100 parts of lead powder; graphene-based polymer slurry, 5; 0.5 part of barium sulfate; 0.1 part of humic acid; 0.05 part of polyester staple fiber; 0.5 part of conductive carbon black; 0.1-5 parts of water (the specific dosage of the water is based on the lead plaster apparent density).
EXAMPLE 8 preparation of Battery plates
The lead paste prepared in example 7 was coated on a lead-tin-calcium grid and cured to obtain a battery plate.
The curing comprises two stages of curing, namely, the first stage of low-temperature high-humidity curing and the second stage of high-temperature curing. The first stage is as follows: curing for 48h under the atmosphere conditions of the temperature of 60 ℃ and the humidity of 90 percent. And a second stage: curing at 105 deg.C for 10min.
EXAMPLE 9 preparation of lead-acid Battery
A lead-carbon battery cell is assembled by using a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, a negative plate (a battery plate prepared in example 8), the glass fibers and the positive plate, and 1.265g/cm of lead-carbon battery cell is injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
Comparative example 1 preparation of lead paste
Mixing raw materials containing lead powder, sodium lignosulphonate, sulfuric acid, barium sulfate, polyester staple fiber, graphene and water, wherein the mass percentages of the components in the raw materials are respectively as follows: 81.7% of lead powder, 0.15% of sodium lignosulfonate, 4% of sulfuric acid, 1% of barium sulfate, 0.1% of polyester staple fiber, 0.05% of graphene (with the particle size of D50=10.0 μm) and 13% of water are mixed and stirred uniformly to prepare the lead-acid battery cathode lead paste.
Comparative example 2 preparation of Battery plates
And (3) coating the lead-acid battery negative lead plaster obtained in the comparative example 1 on a lead-tin-calcium grid, and curing for 24 hours under the atmosphere condition that the temperature is 65 ℃ and the humidity is 40% to obtain the lead-acid battery negative plate.
Comparative example 3 preparation of lead-acid Battery
The lead-acid battery cell is assembled by adopting a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, the negative plate, the glass fibers and the positive plate obtained in the comparative example 2, and 1.265g/cm of lead-acid battery cell is injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
Comparative example 4 preparation of lead paste
Mixing raw materials containing lead powder, sodium lignosulphonate, sulfuric acid, barium sulfate, polyester staple fiber, graphene and water, wherein the mass percentages of the components in the raw materials are respectively as follows: 81.6% of lead powder, 0.15% of sodium lignosulfonate, 4% of sulfuric acid, 1% of barium sulfate, 0.1% of polyester short fiber, 0.05% of graphene (particle size D50=120.0 μm) and 13% of water are uniformly mixed and stirred to prepare the lead-acid battery negative electrode lead paste.
Comparative example 5 preparation of Battery plates
And (3) coating the lead-acid battery negative lead plaster obtained in the comparative example 4 on a lead-tin-calcium grid, and curing for 24 hours under the atmosphere condition that the temperature is 65 ℃ and the humidity is 40% to obtain the lead-acid battery negative plate.
Comparative example 6 preparation of lead-acid Battery
The lead-acid battery cell is assembled by adopting a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, the negative plate, the glass fibers and the positive plate obtained in the comparative example 5, and 1.265g/cm of lead-acid battery cell is injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
Comparative example 7 preparation of lead paste
Step 1 preparation of graphene slurry
The graphene-based polymer slurry was prepared by a chemical oxidation method by adding an initiator solution to an aqueous precursor solution containing a polymer monomer, graphene (particle size D50=2.0 μm), sulfuric acid, and a sulfonate dopant.
Wherein, the precursor solution contains 100 parts of water by weight; 100 parts of sulfuric acid; 20 parts of graphene; 4 parts of pyrrole; 1.2 parts of sodium lignosulfonate; and in the process of preparing the precursor solution, dispersing in a high-speed shearing and stirring mode of 500r/min (the stirring time is not less than 60min, until the dispersion is uniform).
The initiator solution is prepared from water and ammonium persulfate, and comprises the following components in parts by weight: 90 parts of water; ammonium persulfate, 15 parts.
The weight ratio of the initiator solution to the precursor solution is 1:9; the initiator solution was slowly added to the precursor solution using 40 ml/min.
Step 2 preparation of negative lead plaster
The preparation method of the graphene slurry lead-carbon negative electrode lead paste comprises the following steps:
(1) Premixing other raw material components except the graphene-based polymer slurry (without special requirements, mechanically and physically mixing uniformly) to prepare a premixed material; the other raw materials include lead powder, barium sulfate, humic acid (commercially available, commonly used), and short fiber (diameter)
Micron) and conductive carbon black; the preparation process of the premixed material needs to add and mix in a certain sequence, and requires that lead powder, barium sulfate, sodium sulfate and humic acid are added and mixed firstly, then short fibers are added and mixed, and finally conductive carbon black is added and mixed.
(2) Stirring and pasting the graphene-based polymer slurry prepared in the step (1) and the premixed material (the temperature of the paste is controlled within 60 ℃), adding water for regulation during stirring and pasting, and enabling the apparent density of the lead paste to reach 4.32g/cm 3 And (3) obtaining the graphene-based polymer slurry lead-carbon negative electrode lead paste by obtaining the paste according to the following raw materials in parts by mass: 100 parts of lead powder; 5 parts of graphene slurry; 0.5 part of barium sulfate; 0.1 part of humic acid; 0.05 part of polyester staple fiber; 0.5 part of conductive carbon black; 0.1-5 parts of water (the specific dosage of the water is based on the lead plaster apparent density).
Comparative example 8 preparation of Battery plates
And (3) coating the lead-carbon negative lead plaster obtained in the comparative example 7 on a lead-tin-calcium grid, and curing for 48 hours under the atmosphere condition that the temperature is 65 ℃ and the humidity is 60% to obtain the negative plate of the lead-acid battery.
Comparative example 9 preparation of lead-acid Battery
The battery core of the lead-acid battery is assembled by adopting a commercially available positive plate consisting of lead powder, short fibers, red lead and a conductive agent (colloidal graphite) according to the arrangement sequence of the positive plate, glass fibers, a negative plate (a battery plate prepared by a comparative example 8), the glass fibers and the positive plate, and 1.265g/cm of the positive plate, the glass fibers and the positive plate are injected 3 And (4) sealing the battery shell by using sulfuric acid electrolyte to prepare the lead-acid battery.
Test example 1
The strength properties of the cured battery plates prepared in examples 2, 5 and 8 and comparative examples 2, 5 and 8 were compared as shown in table 1.
The method for testing the strength of the battery plate comprises the following steps: weighing the mass of the plate, and recording as m 1 (ii) a Then placing the polar plate in a free falling body impact experiment with the height of 1.5m from the ground, and continuously repeating the experiment for 4 times; then, the mass of the pole plate after the impact test of the free falling body is measured and recorded as m 2 (ii) a Finally, calculating mass reduction ratio of the pole plate before and after the experiment, namely m 2 ÷m 1 ×100％＝t
TABLE 1
| Example (b) | Pole plate strength t |
| Comparative example 2 | 97.0％ |
| Comparative example 5 | 97.5％ |
| Comparative example 8 | 95.8％ |
| Example 2 | 98.1％ |
| Example 5 | 98.5％ |
| Example 8 | 99.2％ |
Test example 2
The high-rate part-state-of-charge cycle life performance and the charge acceptance were compared for the lead-acid batteries prepared in examples 3, 6, 9 and comparative examples 3, 6, 9, as shown in table 2.
The method for testing the cycle life of the high-rate partial charge state of the lead-acid battery comprises the following steps: a battery testing system (model: CT-4008-5V 6A) of Shenzhen New Wille electronics Limited company is adopted to test the high-rate partial charge state cycle life of the battery. The theoretical capacity of the battery is used as a basis, and the 1C current is set as a cycle life test current. (Charge and discharge 60s is one cycle, and the cycle cut-off voltage of the unit cell is 1.75V)
The method for testing the charge acceptance of the lead-acid battery comprises the following steps: reference is made to GB/T23638-2009.
TABLE 2
As can be seen from the data in tables 1 and 2, the lead-acid batteries including the graphene-based polymer pastes prepared in examples 3, 6 and 9 according to the present invention in the lead paste have significantly higher plate strength, high rate part-state-of-charge cycle life and charge acceptance than the lead-acid batteries prepared by the conventional method of comparative example. The graphene-based polymer slurry and the negative plate prepared by the invention are beneficial to improving the strength of the plate of the lead-acid battery, the high-rate partial charge state cycle life and the charge acceptance.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A lead-carbon battery cathode lead plaster is characterized in that,
the feed comprises the following raw materials in parts by weight:
100 parts of lead powder;
5-10 parts of graphene-based polymer;
0.5-1.0 part of barium sulfate;
0.05 to 0.5 portion of humic acid;
0.05 to 0.3 portion of short fiber;
0.01-0.5 parts of conductive carbon black;
0.1-5 parts of water;
the graphene-based polymer is prepared by doping at least one of polypyrrole and polyaniline with lignosulfonate, taking graphene as a framework and doping an adhesive thickener.
2. The lead-carbon battery negative electrode lead paste according to claim 1,
the particle size D50 of the graphene is less than or equal to 2 mu m;
preferably, the particle size D50 of the graphene is 0.5-2 μm;
the lignosulfonate is selected from at least one of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate;
the bonding thickener is at least one selected from sodium carboxymethylcellulose and styrene butadiene rubber.
3. A method for preparing the lead-carbon battery negative electrode lead paste of claim 1 or 2,
the preparation method comprises the following steps:
mixing raw materials I containing lead powder, barium sulfate, humic acid, short fibers and conductive carbon black according to a ratio to obtain a premixed material; and mixing II the slurry containing the graphene-based polymer with the premixed material and water to obtain the lead-carbon battery negative electrode lead paste.
4. The production method according to claim 3,
the preparation method of the slurry containing the graphene-based polymer comprises the following steps:
mixing a water-based precursor solution containing a polymer monomer, graphene, sulfuric acid, a sulfonate dopant and an adhesive thickener with an initiator solution, and preparing the graphene-based polymer-containing slurry by adopting a chemical oxidation method.
Preferably, in the precursor solution, the weight parts of the components are as follows:
100 parts of water;
60-120 parts of sulfuric acid;
10-20 parts of graphene;
1-5 parts of polymer monomer;
0.3-1.5 parts of sulfonate dopant;
0.1-1.0 part of bonding thickening agent;
preferably, the precursor solution is obtained under stirring conditions;
the stirring speed is 1200 r/min-1500 r/min;
preferably, the polymer monomer is selected from at least one of pyrrole and aniline;
the sulfonate dopant is selected from at least one of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate;
the bonding thickener is at least one of sodium carboxymethylcellulose and styrene butadiene rubber;
preferably, the initiator solution comprises the following components in parts by weight:
80-90 parts of water;
10-20 parts of an initiator;
preferably, the initiator is selected from at least one of ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide;
preferably, the weight ratio of the initiator solution to the precursor solution is 1:5-1;
preferably, the initiator solution is added to the precursor solution at a dropping rate of 15ml/min to 25 ml/min.
5. The method according to claim 3,
the preparation method of the premix material comprises the following steps:
(1) Mixing raw materials containing lead powder, barium sulfate, sodium sulfate and humic acid to form a mixture I;
(2) Adding short fibers into the mixture I to form a mixture II;
(3) Adding a carbon material to the mixture II to obtain the premix material.
6. The production method according to claim 3,
the mixing II comprises:
stirring the slurry containing the graphene-based polymer and the premixed material, mixing the slurry and the premixed material, adding water to adjust the mixture, and enabling the apparent density of the lead plaster to reach 4.0-4.6 g/cm 3 And then the paste is obtained.
7. A battery plate, wherein the battery plate comprises lead paste;
the lead paste is at least one of the lead-carbon battery negative electrode lead paste according to any one of claims 1 to 2 or the lead-carbon battery negative electrode lead paste prepared by the preparation method according to any one of claims 3 to 6;
preferably, the battery plate is a battery negative plate.
8. A method of making a battery plate as recited in claim 7, wherein:
the preparation method comprises the following steps:
and coating the lead plaster on a grid, and curing to obtain the battery plate.
9. The method of claim 8,
the grid is selected from at least one of a lead-tin-calcium grid and a continuous rolling continuous pressing alloy lead grid;
preferably, the curing comprises a first stage curing and a second stage curing;
wherein, the process conditions of the first stage curing are as follows: curing for 24-48 h under the atmosphere conditions of 50-80 ℃ and 80-100% of humidity;
the process conditions of the second stage curing are as follows: curing for 5-30 min at 100-120 deg.c.
10. Use of the battery plate according to claim 7 or the battery plate obtained by the preparation method according to any one of claims 8 to 9 in a battery, wherein the battery comprises at least one selected from the group consisting of a lead-acid battery, a lead-carbon battery and a lead-carbon battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117253996A (en) * | 2023-09-21 | 2023-12-19 | 湖南京奥新材料科技有限公司 | Graphene-based lead-carbon battery negative plate and preparation method thereof |
| CN117253996B (en) * | 2023-09-21 | 2024-06-07 | 湖南京奥新材料科技有限公司 | Graphene-based lead-carbon battery negative plate and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870451A (en) * | 2016-05-13 | 2016-08-17 | 超威电源有限公司 | Graphene dispersion solution for lead-acid storage batteries and preparation technology of graphene dispersion solution for lead-acid storage batteries |
| CN107068998A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | Battery electrode containing conducting polymer/graphene and its preparation method and application |
| CN107331834A (en) * | 2017-05-25 | 2017-11-07 | 天能电池集团有限公司 | A kind of lead accumulator cathode lead plaster and preparation method thereof |
| CN109904448A (en) * | 2019-01-24 | 2019-06-18 | 汉和新能源有限公司 | A kind of super alkene macromolecule lead storage battery green plate lead plaster |
| CN111224097A (en) * | 2020-01-16 | 2020-06-02 | 中国科学院福建物质结构研究所 | Lead paste, battery plate and preparation method and application thereof |
-
2022
- 2022-07-07 CN CN202210791820.1A patent/CN115188961A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105870451A (en) * | 2016-05-13 | 2016-08-17 | 超威电源有限公司 | Graphene dispersion solution for lead-acid storage batteries and preparation technology of graphene dispersion solution for lead-acid storage batteries |
| CN107068998A (en) * | 2017-03-21 | 2017-08-18 | 中国科学院福建物质结构研究所 | Battery electrode containing conducting polymer/graphene and its preparation method and application |
| CN107331834A (en) * | 2017-05-25 | 2017-11-07 | 天能电池集团有限公司 | A kind of lead accumulator cathode lead plaster and preparation method thereof |
| CN109904448A (en) * | 2019-01-24 | 2019-06-18 | 汉和新能源有限公司 | A kind of super alkene macromolecule lead storage battery green plate lead plaster |
| CN111224097A (en) * | 2020-01-16 | 2020-06-02 | 中国科学院福建物质结构研究所 | Lead paste, battery plate and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 侯晓东 等: "《汽车拖拉机用铅蓄电池》", 31 January 1981, 北京：中国农业机械出版社, pages: 265 - 270 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117253996A (en) * | 2023-09-21 | 2023-12-19 | 湖南京奥新材料科技有限公司 | Graphene-based lead-carbon battery negative plate and preparation method thereof |
| CN117253996B (en) * | 2023-09-21 | 2024-06-07 | 湖南京奥新材料科技有限公司 | Graphene-based lead-carbon battery negative plate and preparation method thereof |
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