CN111525126B - Positive lead paste for high-binding-force screen punching plate grid and preparation method and application thereof - Google Patents
Positive lead paste for high-binding-force screen punching plate grid and preparation method and application thereof Download PDFInfo
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- CN111525126B CN111525126B CN202010244227.6A CN202010244227A CN111525126B CN 111525126 B CN111525126 B CN 111525126B CN 202010244227 A CN202010244227 A CN 202010244227A CN 111525126 B CN111525126 B CN 111525126B
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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
- H01M4/36—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a positive lead plaster for a high-binding-force screen punching plate grid and a preparation method thereof. The lead plaster is prepared from the following raw materials in percentage by mass: 78-84% of lead powder, 5-8% of red lead, 5.4-8.3% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.5-0.7% of tetrabasic lead sulfate, 0.01-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.15% of sodium percarbonate, 0.1-0.3% of solid alkali and the balance of deionized water. The lead plaster improves the binding force between the lead plaster and the binding force between the lead plaster and a grid through the interaction of all the components, and has great improvement compared with the traditional lead plaster and the process. The battery performance obtained by adopting the grid lead paste is obviously improved, the low-temperature starting performance is good, and the circulation stability is good. And the cost is low, and the environment is friendly.
Description
Technical Field
The invention belongs to the technical field of storage battery chemistry. In particular to positive lead plaster for a high-binding force screen punching plate grid and a preparation method and application thereof, namely the positive lead plaster matched with a storage battery screen punching plate grid process and the preparation method thereof.
Background
The core component of the accumulator is a polar plate, and the performance of the polar plate is directly determined by a grid and lead plaster. In the storage battery, the screen punching plate grid is not easy to combine with lead plaster in the preparation process due to smooth surface and small contact surface. In the traditional process, roughening treatment such as roughening treatment is often carried out on the grating of the light panel, and the roughness of the surface of the grating is increased, so that the bonding strength of the grating and lead paste is enhanced. The bonding force between the grid and the lead plaster is increased by improving the lead plaster, sodium perborate is usually added into the lead plaster, the sodium perborate reacts with the lead plaster in the process of mixing to generate hydrogen peroxide and sodium borate, and the hydrogen peroxide is decomposed to release active oxygen, so that the lead powder is oxidized, the oxidation degree is improved, the curing time is shortened, a stable active substance structure is formed to play a role in deep oxidation, and the bonding force between the active substance and the grid is improved. Therefore, the problem of an interface between the conventional battery grid and a lead paste active substance can be effectively solved by adding the sodium borate lead paste, the binding force between the positive grid and the lead paste is improved, the strength of a polar plate can be improved to a certain extent, and the cycle life of the battery is prolonged. However, the addition of sodium perborate obviously increases the production cost, and the dissolution rate is slow, the efficiency is low, the existence of boron further increases the pollution of the battery to the environment, and the boron has obvious harm to soil, crops and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a positive lead paste for a high-bonding-force screen punching plate grid, and a preparation method and application thereof. The lead plaster improves the binding force of the whole lead plaster and a grid through the interaction of all components, and is greatly improved compared with the traditional lead plaster and the process. The battery performance obtained by adopting the grid lead paste is obviously improved, the low-temperature starting performance is good, and the circulation stability performance is good. And the cost is low, and the environment is friendly.
The invention is realized by the following technical scheme
The positive lead plaster for the high-binding-force screen punching plate grid is prepared from the following raw materials in percentage by mass: 78-84% of lead powder, 5-8% of red lead, 5.4-8.3% of sulfuric acid, 0.05-0.06% of short fibers, 0.2-0.3% of graphene oxide, 0.5-0.7% of tetrabasic lead sulfate, 0.01-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.15% of sodium percarbonate, 0.1-0.3% of solid alkali and the balance of deionized water.
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials in percentage by mass: 78-80% of lead powder, 5-6.5% of red lead, 5.4-7.0% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.5-0.6% of tetrabasic lead sulfate, 0.01-0.02% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.10% of sodium percarbonate and 0.1-0.2% of solid alkali.
The high-binding-force positive lead paste for the screen punching plate grid is prepared from the following raw materials in percentage by mass: 80-84% of lead powder, 6.5-8% of red lead, 7.0-8.3% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.6-0.7% of tetrabasic lead sulfate, 0.02-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.10-0.15% of sodium percarbonate and 0.2-0.3% of solid alkali.
The high-binding-force positive lead paste for the screen punching plate grid is characterized in that the solid alkali can be sodium hydroxide, potassium hydroxide or lithium hydroxide, and preferably is sodium hydroxide.
The high-binding force positive lead paste for the screen punching plate grid is characterized in that the silicon dioxide can be gas-phase silicon dioxide, precipitated silicon dioxide or silica sol; preferably, the fumed silica has an average particle diameter of 50 to 70 μm and a specific surface area of 115 to 145m 2 (ii)/g; the content of silicon dioxide in the precipitated silicon dioxide is more than 98 percent, and the specific surface area is 120 to 170m 2 (ii)/g; the content of silicon dioxide in the silica sol is 40 +/-1%.
The high-binding-force positive lead paste for the screen plate grid is characterized in that the oxidation degree of the lead powder is 73 to 76 percent, and the average grain diameter is 7 to 10 mu m; the length of the short fiber is between 2.7 and 3.3mm, and the diameter is between 20 and 25 mu m; the average thickness of the graphene oxide is 1 to 3nm, the diameter is 3 to 5 mu m, the number of layers is 2 to 5, and the specific surface area is 500 to 600m 2 /g。
The high-binding-force positive lead plaster for the screen punching plate grid is characterized in that the red lead contains more than or equal to 97% of lead tetroxide, more than or equal to 33% of lead dioxide and less than or equal to 0.0005% of iron; preferably, the lead dioxide content in the lead tetraoxide is more than or equal to 33 percent.
The positive lead plaster for the high-binding force screen punching plate grid is characterized in that the granularity of the tetrabasic lead sulfate is the diameter of the lead powder intermediate value<5 microns, water content less than 1%; the density of the sulfuric acid is 1.400g/m 3 (ii) a The zinc oxide has an average particle size of 30 to 50nm and a specific surface area of 20 to 70m 2 Surface characteristics, hydrophilicity.
A preparation method of positive lead paste for a high-binding-force screen punching plate grid comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, silicon dioxide, zinc oxide, sulfuric acid, solid alkali and sodium percarbonate according to the raw material proportion required by the above step;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the silicon dioxide and the zinc oxide in the step 1 into a paste mixer, stirring for 10 to 15min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10 min, and uniformly stirring to obtain a mixture;
(4) Slowly adding a solid alkaline water solution with the mass fraction of 10% into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10 to 15min, and uniformly stirring to obtain a mixture;
(6) And (6) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead paste, and coating the lead paste for 5 min.
The obtained positive lead paste for the high-bonding-force screen punching plate grid has the apparent density of 4.0-4.3g/m 3 The penetration/ring is 20 to 25.
The lead paste obtained by the method is applied to batteries.
Compared with the prior art, the invention has the following positive beneficial effects
In the lead plaster prepared by the invention, sodium percarbonate reacts to generate hydrogen peroxide and sodium carbonate in the paste reaction process, and the hydrogen peroxide is decomposed to release active oxygen, so that lead powder is oxidized to improve the oxidation degree, the curing time is shortened, a stable active substance structure is formed, and the deep oxidation effect is further played, so that the binding force between the active substance and a grid is improved; the sodium percarbonate and the decomposition products thereof have no pollution to the environment and are environment-friendly, so that the influence of the waste battery on the environment is better reduced; in addition, the sodium percarbonate has low price, improves the bonding force between the lead paste and the grid, improves the performance of the battery, reduces the production cost of the battery, and has better practical application effect.
In the process of preparing the lead plaster, an alkaline aqueous solution is added, and hydroxide radical and lead oxide or an additive form a compound (PbO and OH) with strong stable binding force - Ionic complex) so that the bonding force between the lead plaster and the lead plaster is enhanced. And sodium percarbonate is added, so that the corrosion of the surface of the grid is increased, and the binding force of the grid and lead paste is improved.
Drawings
Fig. 1 shows a picture of a screen grid of a lead-coated sheet obtained according to the invention after it has been dropped.
Fig. 2 shows a photograph of a prior art cliche-coated plate after the screen grid has been dropped.
Fig. 3 is a graph showing the cycle life of the invention and paste formulations compared to a conventional paste formulation coated plate screen grid fabricated cell.
Detailed Description
The present invention will be described in more detail with reference to the following embodiments, which are provided for understanding the technical solutions of the present invention, but are not intended to limit the scope of the present invention.
The invention provides a high-binding force positive lead plaster for a screen punching plate grid, which is prepared from the following raw materials in percentage by mass: 78-84% of lead powder, 5-8% of red lead, 5.4-8.3% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.5-0.7% of tetrabasic lead sulfate, 0.01-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.15% of sodium percarbonate, 0.1-0.3% of solid alkali and 8.0-10.5% of deionized water.
The content of the lead powder can be any value between 78% and 84%, such as 78%, 79%, 80%, 81%, 82%, 83% and 84%; the content of the red lead can be any value between 5% and 8%, such as 5%, 6%, 7% and 8%; the content of the sulfuric acid can be any value between 5.4% and 8.3%, such as 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.5%, 7.0%, 7.5%, 8.0%, 8.3%; the content of the short fiber can be any value between 0.05% and 0.06%; the content of the graphene oxide can be any value between 0.2% and 0.3%; the content of the tetrabasic lead sulfate can be any value between 0.5 and 0.7 percent; the content of the silicon dioxide can be any value between 0.01 and 0.03 percent; the content of the zinc oxide can be any value between 0.01% and 0.02%; the content of the sodium percarbonate powder can be any value between 0.05% and 0.15%, such as 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.10%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%; the content of the solid alkali can be any value between 0.1% and 0.3%, such as 0.10%, 0.15%, 0.2%, 0.25%, 0.3%. When in use, the solid alkali is firstly prepared into an alkali solution with the mass fraction of 10% and then used for preparing lead plaster.
In the used raw materials, the oxidation degree of the lead powder is 73-76%, and the average grain diameter is 7-10 μm; the red lead contains more than or equal to 97 percent of lead tetraoxide (the content of lead dioxide in the lead tetraoxide is more than or equal to 33 percent) and less than or equal to 0.0005 percent of iron; the length of the short fiber is between 2.7 and 3.3mm, and the diameter is between 20 and 25 mu m; the average thickness of the graphene oxide is 1 to 3nm, the diameter is 3 to 5 mu m, the number of layers is 2 to 5, and the specific surface area is 500 to 600m 2 (iv) g; the granularity of the tetrabasic lead sulfate is the diameter of the lead powder with the median value<5 microns, water content less than 1%; the density of the sulfuric acid is 1.400g/m 3 (ii) a The zinc oxide has an average particle size of 30 to 50nm and a specific surface area of 20 to 70m 2 Surface characteristics, hydrophilicity.
The solid alkali can be sodium hydroxide, potassium hydroxide or lithium hydroxide, and is preferably sodium hydroxide; are all analytically pure; the purity of the sodium percarbonate is more than 95%. The silicon dioxide can be gas phase silicon dioxide, precipitated silicon dioxide or silica sol; preferably, the fumed silica has an average particle diameter of 50 to 70 μm and a specific surface area of 115 to 145m 2 (iv) g; the content of silicon dioxide in the precipitated silicon dioxide is more than 98 percent, and the specific surface area is 120 to 170m 2 (ii)/g; the content of silicon dioxide in the silica sol is 40 +/-1%.
The lead powder, red lead, sulfuric acid, short fibers, graphene oxide, tetrabasic lead sulfate, silicon dioxide, zinc oxide, sodium percarbonate and solid alkali adopted by the invention are all commercially available and are products well known to those skilled in the art.
The lead plaster prepared by the invention has obviously improved binding force, low cost, environmental friendliness and no pollution to the environment.
The invention also provides a preparation method of the positive lead paste for the high-binding-force screen punching plate grid, which comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, silicon dioxide, zinc oxide, sulfuric acid, solid alkali (prepared into a solid alkali water solution with the mass fraction of 10%) and sodium percarbonate according to the raw material proportion required by the above step;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the silicon dioxide and the zinc oxide in the step 1 into a paste mixer, stirring for 10 to 15min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10 min, and uniformly stirring to obtain a mixture;
(4) Slowly adding a solid alkaline water solution with the mass fraction of 10% into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10 to 15min, and uniformly stirring to obtain a mixture;
(6) And (5) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead plaster, and coating the lead plaster after 5 min.
The method increases the binding force of the lead plaster and the lead plaster by adding the solid alkali solution; sodium percarbonate is added, so that the binding force between the grid and the lead plaster is increased; the binding force of the polar plate is improved, so that the performance of the battery is improved. The cost is reduced, and the battery cost is also reduced; has no pollution to the environment and is environment-friendly.
The invention also provides the prepared high-binding-force positive lead paste for the screen plate grid, and the apparent density of the lead paste is 4.0 to 4.3g/m 3 The penetration/circle is 20 to 25.
The binding force between the lead paste and the grid is obviously enhanced, and the service life and the cycle number of the battery are also obviously improved. And the lead plaster is environment-friendly.
The lead plaster coated plate obtained by the invention is punched into a mesh plate grid, and the lead plaster coated plate obtained by the prior art is punched into the mesh plate grid, so that the falling strength of the two grids is measured. Weighing the mass m of the cured polar plate (removing the two-side coated paper) 0 Then the paste coated surface is downward, and the paste is horizontally and freely dropped on a flat and dry table top from a position with the height of 1 m, the two surfaces are alternated, and after the paste is repeatedly dropped for 8 times, the mass m1 is weighed. Calculating the falling strength delta ss of the pole plate according to the formula:
the calculation result shows that the polar plate dropping strength of the lead plaster mesh punching grid is 2.42%, and the polar plate dropping strength of the lead plaster mesh punching grid in the prior art is 3.46%. The plate falls as shown in fig. 1 and 2. Wherein fig. 1 is a picture of the lead plaster coated plate obtained by the invention after the screen punching plate grid falls off, and fig. 2 is a picture of the lead plaster coated plate obtained by the prior art after the screen punching plate grid falls off.
As can be seen from fig. 1, the slab lattice coated with the lead paste of the present invention has no obvious paste falling phenomenon after falling. As can be seen from fig. 2, the obvious phenomenon of lead paste falling occurs after the grid is coated with the lead paste prepared in the prior art and falls off. And the overall drop strength of the present invention is nearly 25% less than the drop strength of the prior art. Therefore, the lead plaster prepared by the invention has good binding force with the polar plate and the lead plaster of the polar plate, and the binding force is obviously improved.
The invention also provides an application of the lead paste prepared by the method in a battery. The lead plaster obviously improves the bonding force with the grid, so that the performance of the grid is improved. Therefore, the prepared battery has prolonged cycle life, and the preparation process is environment-friendly and pollution-free.
The following is a more detailed description with specific examples.
Example 1
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 7.5Kg of red lead and short fibers0.0625Kg, 0.3125Kg of graphene oxide, 0.625Kg of tetrabasic lead sulfate, 0.01875Kg of fumed silica, 0.01875Kg of zinc oxide, 10Kg of deionized water, 1.25Kg of 10% sodium hydroxide aqueous solution, 1.400g/m 3 6.25Kg of sulfuric acid and 0.09375Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 Needle penetration/ring 22.
Example 2
The positive lead plaster for the high-binding-force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 10Kg of red lead, 0.075Kg of short fiber, 7.5Kg of sulfuric acid with the concentration of 1.400g/m < 3 >, 0.35Kg of graphene oxide, 0.75Kg of tetrabasic lead sulfate, 0.0225Kg of fumed silica, 0.0225Kg of zinc oxide, 12.5Kg of deionized water, 1.5Kg of 10% sodium hydroxide aqueous solution and 0.09375Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 A needle penetration/ring 22.
Example 3
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 6.4Kg of red lead, 0.064Kg of short fibers, 0.2564Kg of graphene oxide, 0.641Kg of tetrabasic lead sulfate, 0.01282Kg of fumed silica, 0.01282Kg of zinc oxide, 10.26Kg of deionized water, 1.282Kg of 10% aqueous sodium hydroxide solution, 6.92Kg of sulfuric acid of 1.400g/m3, 0.0641Kg of sodium percarbonate, and the apparent density of lead paste is adjusted to 4.0 to 4.3g/m 3 A needle penetration/ring 22.
Example 4
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 9.5Kg of red lead, 0.0714Kg of short fiber, 0.3571Kg of graphene oxide, 0.833Kg of tetrabasic lead sulfate, 0.02381Kg of fumed silica, 0.02381Kg of zinc oxide, 12.5Kg of deionized water, 1.786Kg of 10% sodium hydroxide aqueous solution, 1.400g/m 3 7.5Kg of sulfuric acid and 0.1786Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 Needle penetration/ring 22.
Example 5
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 8.1Kg of red lead, 0.08675Kg of short fibers, 0.3125Kg of graphene oxide and 0.75Kg of tetrabasic lead sulfate0.01875Kg of fumed silica, 0.02381Kg of zinc oxide, 11.25Kg of deionized water, 1.5Kg of 10% sodium hydroxide aqueous solution, 1.400g/m 3 7.5Kg of sulfuric acid and 0.125Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 A needle penetration/ring 22.
Example 6
The positive lead plaster for the high-binding force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 7.8Kg of red lead, 0.06627Kg of short fibers, 0.3012Kg of graphene oxide, 0.7229Kg of tetrabasic lead sulfate, 0.02410Kg of precipitated silica, 0.01807Kg of zinc oxide, 11.25Kg of deionized water, 2.4Kg of 10% lithium hydroxide aqueous solution, 1.400g/m 3 7.1Kg of sulfuric acid and 0.1205Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 A needle penetration/ring 22.
Example 7
The positive lead plaster for the high-binding-force screen punching plate grid is prepared from the following raw materials: 100Kg of lead powder, 9.5Kg of red lead, 0.0714Kg of short fiber, 0.3571Kg of graphene oxide, 0.833Kg of tetrabasic lead sulfate, 0.03571Kg of silica sol, 0.02381Kg of zinc oxide, 12.5Kg of deionized water, 3.0Kg of 10% potassium hydroxide aqueous solution, 1.400g/m 3 7.5Kg of sulfuric acid and 0.1786Kg of sodium percarbonate, and the apparent density of the lead paste is adjusted to be 4.0 to 4.3g/m 3 A needle penetration/ring 22.
Example 8
A preparation method of positive lead paste for a high-bonding-force screen punching plate grid comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, precipitated silicon dioxide, zinc oxide, sulfuric acid, lithium hydroxide and sodium percarbonate according to the required raw material proportion;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the precipitated silica and the zinc oxide obtained in the step 1 into a paste mixer, stirring for 10 to 15min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10min, and uniformly stirring to obtain a mixture;
(4) Slowly adding a lithium hydroxide aqueous solution with the mass fraction of 10% into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10 to 15min, and uniformly stirring to obtain a mixture;
(6) And (5) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead plaster, and coating the lead plaster after 5 min.
Example 9
A preparation method of positive lead paste for a high-bonding-force screen punching plate grid comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, silica sol, zinc oxide, sulfuric acid, potassium hydroxide and sodium percarbonate according to the raw material proportion required by the above step;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the silica sol and the zinc oxide in the step 1 into a paste mixer, stirring for 10 to 15min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10 min, and uniformly stirring to obtain a mixture;
(4) Slowly adding 10% by mass of potassium hydroxide aqueous solution into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10 to 15min, and uniformly stirring to obtain a mixture;
(6) And (5) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead plaster, and coating the lead plaster after 5 min.
Example 10
A preparation method of positive lead paste for a high-bonding-force screen punching plate grid comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, fumed silica, zinc oxide, sulfuric acid, sodium hydroxide and sodium percarbonate according to the raw material proportion required by the above step;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the fumed silica and the zinc oxide obtained in the step 1 into a paste mixer, stirring for 10 to 15min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10 min, and uniformly stirring to obtain a mixture;
(4) Slowly adding a 10% sodium hydroxide aqueous solution into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10 to 15min, and uniformly stirring to obtain a mixture;
(6) And (5) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead plaster, and coating the lead plaster after 5 min.
The positive electrode lead paste for the screen punching plate grid is adopted to prepare a battery, and the performance detection is carried out, specifically as follows:
weighing the prepared polar plates, assembling the polar plates into a 60Ah battery according to a positive 6 (punching a positive grid) and a negative 6 (pulling a negative grid), isolating the polar plates by PE (polyethylene) separator paper, and stacking the positive plate and the negative plate in a staggered manner. Injecting sulfuric acid electrolyte into the battery to prepare the battery;
simultaneously preparing a lead plaster battery added with sodium perborate;
the drop strengths of the two plates were compared to the cycle life of the two batteries.
The cycle life of the battery is detected as follows: after the storage battery is subjected to the cycle endurance I tested by 4.8.2 in the national standard GB/T5008.1-2013, the storage battery is completely charged according to 5.2.2 and is kept at the ambient temperature of 25 +/-2 ℃ by a method of 5.2.4.
In the experimental process, the storage battery is tested according to the following steps:
a) The storage battery discharges for 1h at the current of 15A;
b) Then charging for 2h55min at the voltage of 14.40 +/-0.1V, and the maximum current limit is 30 (A);
c) Then the charging current of the exhaust storage battery is 7.5 (A), and the charging is carried out for 5min;
d) The test cycle is completed once by a) to c), the terminal voltage of the storage battery is not lower than 10.50V during cyclic discharge, otherwise, the test is terminated;
e) Performing low-temperature starting discharge at-18 deg.C + -1 deg.C with discharge current of 0.6 at 120 times according to national standard GB/T5008.1-2013-5.5.1In (A), the discharge time is 30s, and the voltage is not lower than 7.2V.
And the storage battery prepared from the positive lead plaster for the grid punching is subjected to charge and discharge circulation according to the circulation system, and the circulation times are recorded. The results are shown in FIG. 3. It can be seen from fig. 3 that the cycle life (280 cycles) of the battery of the lead paste of the present invention is 30 cycles longer than that of the battery (250 cycles) with the addition of sodium perborate (prior art), and the lead paste of the present invention can improve the battery life by about 10%. The raw materials used in the invention are environment-friendly and have low cost. Has good practical application effect.
The reference experiment process of the invention is as follows:
the 5.2.2 process in GB/T5008.1-2013 is as follows: charging is carried out for 20h at the voltage of 14.40V +/-0.10V and the current of 15A under the condition of 25 +/-10 ℃, and then charging is carried out for 4h at the voltage of 1.5A.
The 5.2.4 process in GB/T5008.1-2013 is as follows: during the test, the storage battery is placed in a constant-temperature water bath, the temperature meets the test requirements, and the terminal of the storage battery is higher than the water surface by 15mm to 25mm. If there are several accumulators in the same constant-temp water bath, the distance between accumulator and bath wall should not be less than 25mm.
The 5.5.1 process in GB/T5008.1-2013 is as follows: after the storage battery is completely charged for 24 hours according to 5.2.2, the storage battery is placed in a low-temperature box or a low-temperature chamber which is necessary to be provided with air circulation, the temperature is kept at minus 18 ℃ plus or minus 1 ℃, the time is not less than 24 hours, or when the temperature of any middle lattice of the storage battery reaches minus 18 ℃ plus or minus 1 ℃, the storage battery is discharged within 2 minutes after being taken out from the low-temperature box or the low-temperature chamber as follows:
a) Discharging at Icc (A) (500A is used as current in the test process) for 30s, wherein the change of the current value in the discharging time is not more than +/-0.5%, and respectively recording the terminal voltage of the storage battery when discharging for 10s and 30 s;
b) Then stopping discharging, and standing for 20s;
c) Discharging at 0.6 Icc (A) (300A is used as current in the test process) for 40s, wherein the current change in the discharging time is not more than +/-0.5%, and the battery terminal voltage is recorded at 40 s;
d) All experiments were completed within 90 s.
Claims (9)
1. The positive lead plaster for the high-binding-force screen punching plate grid is characterized by being prepared from the following raw materials in percentage by mass: 78-84% of lead powder, 5-8% of red lead, 5.4-8.3% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.5-0.7% of tetrabasic lead sulfate, 0.01-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.15% of sodium percarbonate, 0.1-0.3% of solid alkali and the balance of deionized water; the solid alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide.
2. The positive electrode lead paste for the high-bonding-force screen punching plate grid according to claim 1, wherein the lead paste is prepared from the following raw materials in percentage by mass: 78-80% of lead powder, 5-6.5% of red lead, 5.4-7.0% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.5-0.6% of tetrabasic lead sulfate, 0.01-0.02% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.05-0.10% of sodium percarbonate, 0.1-0.2% of solid alkali and the balance of deionized water; the solid alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide.
3. The positive electrode lead paste for the high-bonding-force screen punching plate grid according to claim 1, wherein the lead paste is prepared from the following raw materials in percentage by mass: 80-84% of lead powder, 6.5-8% of red lead, 7.0-8.3% of sulfuric acid, 0.05-0.06% of short fiber, 0.2-0.3% of graphene oxide, 0.6-0.7% of tetrabasic lead sulfate, 0.02-0.03% of silicon dioxide, 0.01-0.02% of zinc oxide, 0.10-0.15% of sodium percarbonate, 0.2-0.3% of solid alkali and the balance of deionized water; the solid alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide.
4. The positive electrode lead paste for the high-bonding-force screen punching plate grid according to any one of claims 1 to 3, wherein the silicon dioxide is fumed silica, precipitated silica or silica sol;
the fumed silica has an average particle diameter of 50 to 70 μm and a specific surface area of 115 to 145m 2 (ii)/g; the content of silicon dioxide in the precipitated silicon dioxide is more than 98 percent, and the specific surface area is 120 to 170m 2 (iv) g; the content of silicon dioxide in the silica sol is 40 +/-1%.
5. The positive electrode lead paste for the high-bonding-force screen punching plate grid according to any one of claims 1 to 3, wherein the oxidation degree of the lead powder is 73 to 76%, and the average particle size is 7 to 10 μm; the length of the short fiber is between 2.7 and 3.3mm, and the diameter is between 20 and 25 mu m; the average thickness of the graphene oxide is 1-3 nm, the diameter is 3-5 mu m, the number of layers is 2-5, and the specific surface area is 500-600 m 2 /g。
6. The positive electrode lead paste for the high-bonding-force screen punching plate grid according to any one of claims 1 to 3, wherein the red lead contains more than or equal to 97% of lead tetraoxide and less than or equal to 0.0005% of iron; the lead dioxide content in the lead tetraoxide is more than or equal to 33 percent.
7. The positive electrode lead paste for a high-bonding-force screen punching plate grid according to any one of claims 1 to 3, wherein the sulfuric acid density is 1.400g/m 3 (ii) a The average grain diameter of the zinc oxide is 30-50 nm, and the specific surface area is 20-70 m 2 /g, surface properties, hydrophilicity.
8. The positive electrode lead paste for high-bonding force screen printing plate grid according to claim 1, wherein the lead paste has a visual inspectionThe density is 4.0 to 4.3g/cm 3 The penetration is 20-25 mm.
9. The preparation method of the positive electrode lead paste for the high-bonding-force screen punching plate grid as claimed in any one of claims 1 to 7, wherein the method comprises the following steps:
(1) Preparing raw materials of lead powder, red lead, short fibers, graphene oxide, tetrabasic lead sulfate, silicon dioxide, zinc oxide, sulfuric acid, solid alkali and sodium percarbonate according to a proportion; the solid alkali is sodium hydroxide, potassium hydroxide or lithium hydroxide;
(2) Adding the lead powder, the red lead, the short fibers, the graphene oxide, the tetrabasic lead sulfate, the silicon dioxide and the zinc oxide obtained in the step 1 into a paste mixer, stirring for 10-15 min, and fully and uniformly mixing to obtain a mixed material;
(3) Slowly adding deionized water into the mixed material obtained in the step (2), then stirring for 7-10 min, and uniformly stirring to obtain a mixture;
(4) Slowly adding a solid alkaline water solution with the mass fraction of 10% into the mixture obtained in the step (3), stirring for 5-7 min, and uniformly stirring to obtain a mixture;
(5) Slowly adding a sulfuric acid solution into the mixture obtained in the step (4), stirring for 10-15 min, and uniformly stirring to obtain a mixture;
(6) And (5) cooling the mixture obtained in the step (5) to below 49 ℃, adding sodium percarbonate into the mixture, uniformly stirring to obtain the lead plaster, and coating the lead plaster after 5 min.
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| CN112510182B (en) * | 2020-12-08 | 2022-03-11 | 广东奥克莱集团有限公司 | Lead paste for lead-acid storage battery and lead-acid storage battery |
| CN113611852B (en) * | 2021-06-25 | 2022-11-29 | 骆驼集团蓄电池研究院有限公司 | Positive and negative pole lead plaster of lead-acid storage battery |
| CN113644270A (en) * | 2021-08-11 | 2021-11-12 | 河南超威电源有限公司 | High-capacity positive lead paste and preparation method thereof |
| CN114068916B (en) * | 2021-10-19 | 2023-04-18 | 广东奥克莱集团有限公司 | Maintenance-free lead-acid storage battery positive lead paste and preparation method thereof |
| CN114267835A (en) * | 2021-12-28 | 2022-04-01 | 河南超威正效电源有限公司 | Lead paste of lead-acid storage battery, preparation method of lead paste, pole plate and curing process of pole plate |
| CN114824249A (en) * | 2022-05-24 | 2022-07-29 | 天能电池集团股份有限公司 | Lead storage battery positive plate lead paste and preparation method thereof, and lead storage battery |
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