CN112436143B - Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery - Google Patents
Preparation method of negative electrode lead paste and negative electrode plate of lead-acid storage battery Download PDFInfo
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Abstract
The negative lead plaster of the lead-acid storage battery comprises the following components in percentage by mass: short fiber: lignin: humic acid: barium sulfate: barium-doped carbon nitride: carbon material: purified water: dilute sulfuric acid = 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0): (10-15): (6-10). The barium-doped carbon nitride additive is added into the negative lead plaster, so that the sulfation of a negative plate can be avoided, and the service life of a lead-acid battery can be prolonged; the negative plate prepared by the method has higher partial charge state cycle life and static charge acceptance capacity than the common negative plate.
Description
Technical Field
The invention relates to a lead paste for a negative electrode of a lead-acid storage battery and a preparation method of the negative electrode plate, belonging to the technical field of lead-acid storage batteries.
Background
With the rapid development of economy and the improvement of the living standard of people in China, the automobile holding capacity is higher and higher, and particularly, the automobile can be started for many times in the driving process at the early and late peak of a city. This results in the lead-acid battery in the automobile being in an uncharged partial state of charge for a long time, which affects the service life of the lead-acid battery.
Generally, a lead-acid battery is mainly composed of a positive electrode plate, a negative electrode plate, an electrolyte, a separator, and a case. The polar plate prepared by coating the lead paste on the grid plays an important role in the electrical performance of the lead-acid battery. In the negative electrode of lead-acid batteryThe main active material is spongy lead, and when the battery discharges, the lead cathode is used as an anode, and simple substance lead is oxidized into Pb2+And with SO in the electrolyte4 2-Reaction takes place to form PbSO with very low solubility4And deposited into the negative plate.
When the lead-acid battery is in an incompletely charged partial charge state for a long time, PbSO in a negative plate is easily caused4And the crystal grains continuously grow into complete and coarse crystal grains, so that the electrochemical activity of the crystal grains is reduced, and the service life of the battery is prolonged. This phenomenon is known in the industry as "negative plate sulfation". To alleviate this phenomenon, various swelling agents are generally added to the negative electrode. At present, commonly used negative electrode expanding agents are divided into organic expanding agents and inorganic expanding agents, wherein the organic expanding agents mainly comprise lignosulphonate, humic acid, tanning agents and the like, and the main purpose is to ensure that a negative electrode active substance has a larger specific surface area; the inorganic expanding agent is mainly carbon black, barium sulfate, stannous sulfate and the like, not only keeps larger specific surface area of the negative electrode, but also plays a role in refining lead sulfate crystal grains, and improves the conductivity of the active substance to a certain extent.
In the current industry, the negative pole lead plaster formula of the classical starting lead-acid battery comprises basic raw materials such as lead powder, pure water, dilute sulfuric acid and the like, and additives such as short fibers, barium sulfate, sodium lignosulphonate, humic acid, carbon black and the like. However, under the current severer operating conditions of the lead-acid battery, the sulfation resistance of the negative electrode and the service life of the lead-acid battery are required to be further improved.
Disclosure of Invention
The invention provides a preparation method of a negative lead plaster and a negative plate of a lead-acid storage battery, aiming at overcoming the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the negative lead plaster of the lead-acid storage battery comprises the following components in percentage by mass: short fiber: lignin: humic acid: barium sulfate: barium-doped carbon nitride: carbon material: purified water: dilute sulfuric acid 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0): (10-15): (6-10).
According to the lead paste for the negative electrode of the lead-acid storage battery, the main component of the barium-doped carbon nitride is graphite-phase carbon nitride, the barium element is a nucleating agent, the average particle size of the barium-doped carbon nitride is less than 5 mu m, and the specific surface area of the barium-doped carbon nitride is 10-500m2The preparation method comprises the following steps:
weighing a certain amount of Ba (OH)2Adding into solvent, stirring thoroughly to dissolve completely to obtain Ba (OH)2Solution of Ba (OH)2The concentration of the solution is 0.01-5 wt%;
② weighing a certain amount of melamine, adding into Ba (OH)2Obtaining a barium-doped melamine precursor turbid solution, namely melamine and Ba (OH)2The mass ratio of (A) is controlled to be 100: (0.1-10), fully stirring the turbid solution for 0.1-300min, and standing for 0.1-12 h;
thirdly, drying the well-standing barium-doped melamine precursor turbid liquid for 1 to 24 hours at the temperature of between 40 and 120 ℃ to obtain barium-doped melamine precursor powder;
heating the obtained barium-doped melamine precursor powder to 400-800 ℃, and roasting for 0.5-6h at the same time to obtain barium-doped carbon nitride particles;
and fifthly, grinding the obtained barium-doped carbon nitride particles to obtain the barium-doped carbon nitride material for the lead-acid battery.
In the step I, the solvent is one or more of methanol, ethanol and water.
In the fourth step, the barium-doped melamine precursor powder is placed in a crucible with a cover during roasting, or is in a protective atmosphere which is CO2、N2One or more of He and Ar.
According to the lead-acid storage battery negative electrode lead plaster, the oxidation degree of lead powder is 60-98%, wherein the mass ratio of PbO to Pb is (60-98): (40-2).
According to the lead-acid storage battery negative electrode lead plaster, the short fibers are one or more of acrylic fibers, polyester fibers and polyacrylonitrile fibers, and the length of the short fibers is 1-15 mm.
According to the lead-acid storage battery negative electrode lead plaster, the conductivity of the purified water is less than or equal to 0.33 mu s/cm, the dilute sulfuric acid is analytically pure, and the density of the dilute sulfuric acid is 1.1-1.6g/cm3。
According to the lead-acid storage battery negative electrode lead plaster, the carbon material is one or more of carbon black, activated carbon and graphite.
A preparation method of a negative plate, which is used for preparing the negative plate by using the lead paste of the negative electrode of the lead-acid storage battery, comprises the following steps:
firstly, mixing lead powder, short fibers, lignin, humic acid, barium sulfate, barium-doped carbon nitride and a carbon material according to the weight ratio of 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0) stirring and mixing uniformly;
adding water and sulfuric acid aqueous solution into the mixture obtained in the step I in sequence, and fully stirring for 1-30min respectively to obtain lead plaster;
and thirdly, flatly scraping and coating the lead plaster on the grid, wherein the thickness of the lead plaster is 0.5-10mm, the lead plaster is cured for 1-50 h at 20-80 ℃, the relative humidity in the curing process is 90-100%, and then the lead plaster is dried for 0.5-24h at 50-100 ℃, and the relative humidity in the drying process is 0-20%, so as to obtain the negative plate.
In the preparation method of the negative plate, the density of the negative lead paste obtained in the step II is 3.5-4.5g/cm3。
The invention has the beneficial effects that:
the barium-doped carbon nitride additive is added into the negative lead plaster, so that the sulfation of a negative plate can be avoided, and the service life of the lead-acid battery can be prolonged. The storage battery prepared by the method has higher partial charge state cycle life and static charge acceptance capacity than the common storage battery (barium-doped carbon nitride is not added in the negative lead paste), for example, the charge acceptance capacity of the battery at 0 ℃ is improved by 4-5% and the continuous cycle life of 17.5% is improved by more than 25% under the condition that the discharge capacity is not reduced.
The barium-doped carbon nitride of the inventionThe preparation method of the material comprises the steps of directly using melamine as a carbon source and a nitrogen source, uniformly distributing Ba element by an impregnation method, drying and roasting at high temperature to realize the doping of the Ba element in the carbon nitride in one step to obtain the barium-doped carbon nitride material, and avoiding introducing elements such as Fe, Co, Ni and the like and Cl which can cause adverse effects on the lead-acid battery-、NO3 -And (3) plasma. The preparation process omits the procedures of acid washing, alkali washing and the like of the material, reduces energy consumption and water consumption, and reduces cost.
Drawings
FIG. 1 is an XRD test pattern of a barium-doped carbon nitride material;
FIG. 2 is a photograph showing the distribution of elements in a barium-doped carbon nitride material (A is a photograph taken by an electron microscope showing the whole structure, B is a C element distribution, C is an N element distribution, and D is a Ba element distribution);
FIG. 3 shows the result of EDX spectroscopy analysis of a barium-doped carbon nitride material.
Detailed Description
g-C3N4Is a typical polymer semiconductor, and there are two main chemical structures. Triazine ring (C)3N3) g-C as a structural unit3N4Belongs to R3m space group, and the other is 3-s-triazine ring (C)6N7) g-C as a structural unit3N4Belonging to the P6m2 space group. In both structures, the C, N atom generates sp2 hybridization, and a large pi bond similar to a benzene ring structure is formed through a lone pair of electrons on a pz orbit to form a highly delocalized conjugated system. Due to g-C3N4The catalyst has unique electronic structure and thermodynamic stability, has very suitable semiconductor band edge positions, excellent high temperature resistance, acid and alkali resistance and good specific surface area, and is very suitable to be used as a carrier of a nonmetal catalyst, a metal catalyst and a nucleating agent.
The barium-doped carbon nitride added in the lead-acid battery cathode additive mainly comprises g-C3N4g-C of the invention3N4Refers to graphite phase carbon nitride, and is doped with Ba element as a lead sulfate nucleating agent, the Ba element is in sulfuric acid electrolyte environment and in electrolyteSO4 2-Reaction takes place at g-C3N4Surface generation of tiny BaSO4。g-C3N4Surface BaSO4When the negative plate of the lead-acid battery is subjected to anodic oxidation reaction, the lead-acid battery can be used as PbSO4Of the nucleating agent of PbSO4In g-C3N4The surface of the material is dispersedly grown, and the formation of overlarge PbSO is avoided4Grains and reduced electrochemical activity. At the same time, due to g-C3N4The catalytic activity of the material per se reduces the energy barrier of local reduction reaction and promotes nearby free Pb when the negative plate of the lead-acid battery generates cathode reduction reaction2+Reduction to Pb and further slowing down due to PbSO4The reaction difficulty caused by the reduction of the electrochemical activity of the crystal grains is beneficial to avoiding the sulfation of the negative plate, and the effect of prolonging the service life of the lead-acid battery is achieved.
The present invention will be further described with reference to the following examples.
The invention utilizes melamine as a main precursor to obtain g-C through high-temperature solid-phase reaction3N4Predominantly thermodynamically more stable 3-s-triazine ring (C)6N7) g-C as a structural unit3N4. The preparation process comprises the following steps:
weighing a certain amount of Ba (OH)2Adding into solvent, stirring thoroughly to dissolve completely to obtain Ba (OH)2Solution of Ba (OH)2The concentration of the solution is 0.01-5 wt%; the solvent is one or more of methanol, ethanol and water.
② weighing a certain amount of melamine, adding into Ba (OH)2Obtaining a barium-doped melamine precursor turbid solution, namely melamine and Ba (OH)2The mass ratio of (A) is controlled to be 100: (0.1-10), fully stirring the turbid solution for 0.1-300min, and standing for 0.1-12 h;
thirdly, drying the well-standing barium-doped melamine precursor turbid liquid for 1 to 24 hours at the temperature of between 40 and 120 ℃ to obtain barium-doped melamine precursor powder;
fourthly, heating the obtained barium-doped melamine precursor powder to 400-800 ℃, and roasting for 0.5-6h under heat preservation,obtaining barium-doped carbon nitride particles; during roasting, barium-doped melamine precursor powder is placed in a crucible with a cover or in a protective atmosphere of CO2、N2One or more of He and Ar.
And fifthly, grinding the obtained barium-doped carbon nitride particles to obtain the barium-doped carbon nitride material for the lead-acid battery, wherein the average particle size of the barium-doped carbon nitride particles is less than 5 microns.
The method for preparing the negative plate comprises the following steps:
firstly, mixing lead powder, short fibers, lignin, humic acid, barium sulfate, barium-doped carbon nitride and a carbon material according to the weight ratio of 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0) stirring and mixing uniformly;
secondly, water and sulfuric acid aqueous solution are sequentially added into the mixture obtained in the step I, and the mixture is respectively and fully stirred for 1 to 30min to obtain negative pole lead paste, wherein the density of the negative pole lead paste is 3.5 to 4.5g/cm3；
And thirdly, flatly scraping and coating the lead plaster on the grid, wherein the thickness of the lead plaster is 0.5-10mm, the lead plaster is cured for 1-50 h at 20-80 ℃, the relative humidity in the curing process is 90-100%, and then the lead plaster is dried for 0.5-24h at 50-100 ℃, and the relative humidity in the drying process is 0-20%, so as to obtain the negative plate.
The addition ratio of the barium-doped carbon nitride in the negative lead plaster is controlled, because the barium-doped carbon nitride material mainly acts as a nucleating agent and a stable catalyst, if the addition ratio is too small, the barium-doped carbon nitride can not be uniformly and effectively dispersed in the lead plaster, and the effect of prolonging the service life of the battery can not be achieved; if the addition amount is too large, the risk of gas evolution of the polar plate is increased due to the catalyst property of the carbon nitride, and the specific energy of the polar plate is obviously reduced because the material is not used as a substance for electrochemical reaction.
Example 1
1000g of lead powder with the oxidation degree of 80 percent, 3g of barium-doped carbon nitride additive, 0.6g of polyester fiber with the length of 3mm, 2.0g of sodium lignosulfonate, 3.0g of humic acid, 5.0g of fine barium sulfate and 2.0g of carbon material are uniformly mixed, 110g of pure water and 85g of dense carbon material are addedThe degree is 1.4g/cm3Stirring the dilute sulfuric acid to obtain required negative lead paste, preparing a negative plate according to the method, matching and welding the negative plate, the positive plate and a PE diaphragm, and forming to obtain the lead-acid monomer battery of 2V12Ah, wherein the number of the positive plate and the negative plate is 3, the number of the negative plate and the positive plate is 2, the battery number is 1#, and the charging acceptance capacity at 0 ℃ for 20hr and the continuous 17.5% cycle life test are carried out. The results of the experiment are shown in Table 1.
Example 2
1000g of lead powder with the oxidation degree of 80 percent, 5g of barium-doped carbon nitride additive, 0.6g of polyester fiber with the length of 3mm, 2.0g of sodium lignosulfonate, 3.0g of humic acid, 5.0g of fine barium sulfate and 2.0g of carbon material are uniformly mixed, 110g of pure water and 85g of pure water with the density of 1.4g/cm are added3Stirring the dilute sulfuric acid to obtain required negative lead paste, preparing a negative plate according to the method, matching and welding the negative plate, the positive plate and a PE diaphragm, and forming to obtain the lead-acid monomer battery of 2V12Ah, wherein the number of the positive plate and the negative plate is 3, the number of the negative plate and the positive plate is 2, the battery number is 2#, and the charging acceptance capacity at 0 ℃ for 20hr and the continuous 17.5% cycle life test are carried out. The results of the experiment are shown in Table 1.
Comparative example 1
Mixing 1000g of lead powder with oxidation degree of 80%, 0.6g of polyester fiber with length of 3mm, 2.0g of sodium lignosulfonate, 3.0g of humic acid, 5.0g of fine barium sulfate and 2.0g of carbon material uniformly, adding 110g of pure water and 85g of pure water with density of 1.4g/cm3Stirring the dilute sulfuric acid to obtain required negative lead paste, preparing a negative plate according to the method, matching and welding the negative plate, the positive plate and a PE diaphragm, and forming to obtain the lead-acid monomer battery of 2V12Ah, wherein the number of the positive plate and the negative plate is 3, the number of the negative plate and the positive plate is 2, the battery number is 3#, and the charging acceptance capacity at 20hr and 0 ℃ and the continuous 17.5% cycle life test are carried out. The results of the experiment are shown in Table 1.
Table 1 comparison of the performance of the batteries made in example 1, example 2 and comparative example 1
| Battery numbering | 20hr volume (Ah) | 0 ℃ Charge acceptance (A) | Continuous 17.5 Life (time) |
| 1# | 12.56 | 3.67 | 1316 |
| 2# | 12.62 | 3.65 | 1349 |
| 3# | 12.55 | 3.49 | 1077 |
As can be seen from Table 1, the lead-acid battery manufactured by adopting the negative lead paste formula of the invention has the advantages that the charge acceptance at 0 ℃ is improved by 4-5% and the continuous cycle life of 17.5% is improved by more than 25% under the condition of ensuring that the discharge capacity is not reduced.
Example 3
3.0g of Ba (OH) were weighed2Adding into 100g of purified water, stirring thoroughly until completely dissolved to obtain Ba (OH)2And (3) solution. 10.0g of melamine were weighed out and added to Ba (OH)2And (4) obtaining a barium-doped melamine precursor turbid solution in the solution. Stirring the turbid solution for 10min, and standing for 2 h. Drying the well-standing barium-doped melamine precursor turbid liquid at 100 ℃ for 24 hours to obtain barium-doped melamineAmine precursor powder. And heating the obtained barium-doped melamine precursor powder to 550 ℃, and carrying out heat preservation and roasting for 2.0h to obtain barium-doped carbon nitride particles. Placing precursor powder in crucible with cover and in CO during roasting2Under a protective atmosphere. And grinding the obtained barium-doped carbon nitride particles into powder with the average particle size of less than 5 mu m to obtain the barium-doped carbon nitride material for the lead-acid battery.
XRD, SEM and EDX observation analysis are carried out on the obtained barium-doped carbon nitride material, and the results are shown in figures 1-3. FIG. 1 is an XRD test chart of a barium-doped carbon nitride material in which a peak at a diffraction angle of 27.7 ℃ is assigned to g-C3N4The characteristic peak of the (002) crystal face stacked between the aromatic rings corresponds to d ═ 0.323nm, and the other peak at 13.0 ° corresponds to the characteristic peak of the 3-s-triazine structure. It can be shown that the g-C of the material is mainly of 3-s-triazine structure3N4And the substance has no characteristic peak of the separate Ba element because the Ba element is in dispersed doping in the substance.
In fig. 2, a is an SEM observation photograph of the barium-doped carbon nitride material, and in fig. 2, B, C, D is an element distribution diagram of C element, N element, and Ba element, respectively. It can be seen that the material is a fine powder solid material, and the C, N and Ba elements are uniformly distributed in the material, which can further prove that the Ba element in the material is uniformly dispersed.
FIG. 3 shows the EDX spectrum and the quantitative calculation of the barium-doped carbon nitride material. It was further confirmed that the element contained a certain amount of Ba element. The presence of C, N and O in air in large amounts results in slightly higher spectral results at the sample surface.
Claims (10)
1. The lead-acid storage battery negative pole lead plaster is characterized in that: the negative lead plaster comprises the following components in percentage by mass: short fiber: lignin: humic acid: barium sulfate: barium-doped carbon nitride: carbon material: purified water: dilute sulfuric acid 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0): (10-15): (6-10); the barium-doped carbon nitride comprises graphite-phase carbon nitride as a main component.
2. The lead-acid battery negative electrode lead paste of claim 1, wherein: the barium-doped carbon nitride mainly comprises graphite-phase carbon nitride, barium is a nucleating agent, the average grain diameter of the barium-doped carbon nitride is less than 5 mu m, and the specific surface area of the barium-doped carbon nitride is 10-500m2The preparation method comprises the following steps:
weighing a certain amount of Ba (OH)2Adding into solvent, stirring thoroughly to dissolve completely to obtain Ba (OH)2Solution of Ba (OH)2The concentration of the solution is 0.01-5 wt%;
② weighing a certain amount of melamine, adding into Ba (OH)2Obtaining a barium-doped melamine precursor turbid solution, namely melamine and Ba (OH)2The mass ratio of (A) is controlled to be 100: (0.1-10), fully stirring the turbid solution for 0.1-300min, and standing for 0.1-12 h;
thirdly, drying the well-standing barium-doped melamine precursor turbid liquid for 1 to 24 hours at the temperature of between 40 and 120 ℃ to obtain barium-doped melamine precursor powder;
heating the obtained barium-doped melamine precursor powder to 400-800 ℃, and roasting for 0.5-6h at the same time to obtain barium-doped carbon nitride particles;
and fifthly, grinding the obtained barium-doped carbon nitride particles to obtain the barium-doped carbon nitride material for the lead-acid battery.
3. The lead-acid battery negative electrode lead paste of claim 2, wherein: the solvent is one or more of methanol, ethanol and water.
4. The negative lead paste for lead-acid storage batteries according to claim 3, characterized in that: in the fourth step, the barium-doped melamine precursor powder is placed in a crucible with a cover during roasting, or is in a protective atmosphere which is CO2、N2One or more of He and Ar.
5. The lead-acid battery negative electrode lead paste of claim 4, wherein: the oxidation degree of the lead powder is 60-98%, wherein the mass ratio of PbO to Pb in one hundred parts by weight of the lead powder is (60-98): (40-2).
6. The negative lead paste for lead-acid storage batteries according to claim 5, characterized in that: the short fiber is one or more of polyester fiber and polyacrylonitrile fiber, and the length of the short fiber is 1-15 mm.
7. The lead-acid battery negative electrode lead paste of claim 6, wherein: the conductivity of the purified water is less than or equal to 0.33 mu s/cm, the dilute sulfuric acid is analytically pure, and the density of the dilute sulfuric acid is 1.1-1.6g/cm3。
8. The negative lead paste for lead-acid storage batteries according to claim 7, characterized in that: the carbon material is one or more of carbon black, activated carbon and graphite.
9. A preparation method of a negative plate is characterized by comprising the following steps: preparing a negative plate using the negative lead paste for a lead-acid battery of any one of claims 1 to 8, comprising the steps of:
mixing lead powder, short fiber, lignin, humic acid, barium sulfate and barium doped carbon nitride and carbon material according to the weight ratio of 100: (0.05-0.5): (0-1.0): (0-1.0): (0-2.0): (0.1-1.0): (0-1.0) stirring and mixing uniformly;
adding water and a sulfuric acid aqueous solution into the mixture obtained in the step I in sequence, and fully stirring for 1-30min respectively to obtain negative lead paste;
and thirdly, flatly scraping and coating the lead plaster on the grid, wherein the thickness of the lead plaster is 0.5-10mm, the lead plaster is cured for 1-50 h at 20-80 ℃, the relative humidity in the curing process is 90-100%, and then the lead plaster is dried for 0.5-24h at 50-100 ℃, and the relative humidity in the drying process is 0-20%, so as to obtain the negative plate.
10. The production method of the negative plate as claimed in claim 9, characterized in that: the density of the negative pole lead paste obtained in the step II is 3.5-4.5g/cm3。
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