CN111261839A - Deep-cycle power battery positive plate and preparation method thereof - Google Patents
Deep-cycle power battery positive plate and preparation method thereof Download PDFInfo
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- CN111261839A CN111261839A CN202010104272.1A CN202010104272A CN111261839A CN 111261839 A CN111261839 A CN 111261839A CN 202010104272 A CN202010104272 A CN 202010104272A CN 111261839 A CN111261839 A CN 111261839A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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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Abstract
The invention discloses a deep-cycle power battery positive plate, which comprises a positive plate grid and a positive active substance, wherein the structure of the positive plate grid is designed by adopting a radiation type structure; preparing a positive grid from the lead-calcium-tin-silver-selenium-lanthanum aluminum alloy through a process of belt making and net punching; adding acrylic staple fiber, active carbon, tetrabasic lead sulfate, red lead, antimony trioxide, titanium dioxide, stannous sulfate, porous glass beads, distilled water and dilute sulfuric acid into oxidized lead powder according to a formula ratio to serve as raw materials, and preparing the raw materials into a positive active substance by adopting a paste mixing process; and filling the prepared positive active substance on a positive grid, and then sending the positive active substance into a high-temperature curing chamber for curing to prepare the deep-cycle power battery positive plate. The positive plate prepared by the invention has the characteristics of high power, small internal resistance and long battery deep cycle life.
Description
Technical Field
The invention relates to the technical field of lead storage batteries, in particular to a positive plate of a deep-cycle power battery.
Background
With the development of science and technology and the continuous improvement of people's living standard, electric tools and electric equipment are more and more popularized, such as electric ascending vehicles, electric cranes, electric cleaning vehicles and the like. The core component of these vehicles, the power battery, also depends primarily on the import of flooded power batteries from the united states. Therefore, such battery maintenance is troublesome, users lack knowledge of maintenance or management is not in place, and battery life is greatly reduced. By tracking the use working conditions of corresponding vehicle types and carrying out anatomical analysis on batteries after the service life of domestic power batteries is ended after application, the vehicle is generally considered to have the phenomena of high discharge power, deep cycle depth, irregular charge and discharge, violent use and overdischarge.
In the prior art, the conventional battery positive plate used for the vehicle is easy to have polarization internal resistance under the condition of large-current discharge, the corrosion resistance of the positive plate grid is usually more common, the positive active substance is easy to soften and fall off, and the binding force between the positive plate grid and the positive active substance is also common; therefore, the positive plate of the battery has low mechanical strength, general consistency of the manufactured battery, short deep cycle life of the battery and large contact resistance of an active material grid.
For this reason, a new technical solution needs to be designed to solve the above problems.
Disclosure of Invention
In view of the above situation, the invention discloses a deep cycle power battery positive plate and a preparation method thereof.
The technical scheme of the invention is as follows:
the positive plate of the deep-cycle power battery comprises a positive plate grid and a positive active substance, wherein the positive plate grid adopts a radiation type structural design, the positive plate grid specifically comprises a frame, a lug arranged on the frame, and a main inclined rib, a sub inclined rib and a transverse rib which are arranged in the frame, and the main inclined ribs which are separated in pairs are radiated to form the sub inclined ribs in a mode of dividing the main inclined ribs into two parts in the interval range of the two transverse ribs in the middle position of the frame.
Preferably, the upper and lower surfaces of the frame, the main diagonal rib, the sub diagonal ribs and the transverse rib are all provided with knurls.
Preferably, the positive grid is made of a lead-calcium-tin-silver-selenium-lanthanum-aluminum alloy, and the positive grid comprises the following components in percentage by weight: 0.05-0.10% of calcium, 0.8-1.5% of tin, 0.001-0.004% of silver, 0.02-0.10% of selenium, 0.02-0.08% of lanthanum, 0.03-0.05% of aluminum and the balance of lead.
Preferably, the positive grid is manufactured by adopting a belt manufacturing and net punching preparation process, the lead-calcium-tin-silver-selenium-lanthanum-aluminum alloy is firstly melted, a lead belt with the width of 380mm and the thickness of 0.8mm is prepared through multi-stage rolling, then the grid is prepared by utilizing net punching equipment (punching equipment or punching equipment sold in the market can be selected), pollutants on the surface of the grid are cleaned by using ultrasonic waves after the net punching, and meanwhile, knurling is added on the surface of the grid, namely, the roughening treatment is carried out.
Preferably, the positive electrode active material includes, by mass: lead powder with the oxidation degree of 72-85%, acrylic staple fiber 0.07-0.15%, active carbon 0.3-0.6%, tetrabasic lead sulfate 1-5%, red lead 5-15%, antimony trioxide 0.08-0.2%, titanium dioxide 0.05-0.1%, stannous sulfate 0.08-0.2%, porous glass micro-beads 0.3-1%, distilled water 10-15%, and dilute sulfuric acid 8-10% with the density of 1.450 g/ml.
Preferably, the preparation process of the positive electrode active material comprises the following steps: putting the lead powder, acrylic staple fiber, activated carbon, tetrabasic lead sulfate, red lead, antimony trioxide, titanium dioxide, stannous sulfate and porous glass beads in a formula amount into a vacuum paste mixing machine for dry stirring for 2-5 min, then quickly adding distilled water in the formula amount, continuously stirring for 3-5 min, adding dilute sulfuric acid in the formula amount of 1.450g/ml for 4 times, controlling the vacuum degree in the process, controlling the reaction to be kept for 5min at the temperature of 75-80 ℃ by utilizing the heat generated by the reaction of the sulfuric acid and the lead oxide, finally stirring for 3-5 min, testing the apparent specific gravity of 4.3-4.6 g/cm3, and mixing the paste.
Preferably, the vacuum degree during four times of adding the dilute sulfuric acid is controlled as follows: 380mbar, 330mbar, 280mbar and 260 mbar.
A preparation method of a deep cycle power battery positive plate comprises the steps of filling the prepared positive active substance on a positive grid by adopting continuous plate coating equipment according to the standard of 380 +/-5 g, putting 15-20 positive grids in a stacking mode, and conveying the positive grids into a high-temperature curing chamber for curing, wherein the curing process is as follows:
and after solidification, testing that the water content in the active substance of the positive plate is less than or equal to 0.5 percent, the free lead content is less than or equal to 8 percent, and finishing the preparation of the positive plate.
The invention has the beneficial effects that: the positive plate grid adopts a radiation type structural design, so that the polarization internal resistance of the positive plate under the condition of large-current discharge is effectively reduced; the positive grid adopts a preparation process of belt making and net punching, the alloy of the positive grid is subjected to multi-stage rolling, the material is compact, the corrosion resistance of the positive grid can be effectively improved, knurling is added on the surface of the positive grid, the binding force between the positive grid and positive active substances can be effectively improved, and the contact resistance between the grid and the positive active substances is reduced; the positive active substance prepared by the formula and the paste mixing process has the characteristics of high porosity, low shrinkage-expansion ratio of the positive active substance under deep circulation and difficult softening and falling of the positive active substance; the positive plate prepared by the invention has the characteristics of high power, small internal resistance and long battery deep cycle life; compared with the common battery, the finished battery manufactured by the manufactured positive plate according to the container formation battery production process has the advantages of high mechanical strength of the positive plate, good battery consistency, small contact resistance of an active material grid and long deep cycle life of the battery.
Drawings
Fig. 1 is a schematic structural diagram of a positive grid of the present invention.
Fig. 2 is a partially enlarged view of fig. 1.
Wherein: 1. the electrode lug is 2, the main inclined rib is 3, the sub inclined rib is 4, the frame is 5, the transverse rib is 6 and the knurl is formed.
Detailed Description
Example 1
As shown in fig. 1 and 2, the deep cycle power battery positive plate comprises a positive plate grid and a positive active material, wherein the positive plate grid adopts a radiation type structural design, the positive plate grid specifically comprises a frame 4, a tab 1 arranged on the frame 4, and a main diagonal rib 5, a sub diagonal rib 3 and a transverse rib 5 which are arranged in the frame 4, and the sub diagonal ribs 3 are formed by radiation in a manner of dividing two main diagonal ribs 2 which are spaced in pairs into two parts within the interval range of the two transverse ribs 5 on the middle position of the frame.
The positive grid is made of a lead-calcium-tin-silver-selenium-lanthanum aluminum alloy material, and the positive grid comprises the following components in percentage by weight: 0.08 percent of calcium, 0.125 percent of tin, 0.25 percent of silver, 0.02 percent of selenium, 0.03 percent of lanthanum and 0.035 percent of aluminum.
The positive grid is manufactured by adopting a belt manufacturing and net punching preparation process, firstly, a lead-calcium-tin-silver-selenium-lanthanum-aluminum alloy is melted, a lead belt with the width of 380mm and the thickness of 0.8mm is prepared through multi-stage rolling, then, a grid is prepared by utilizing net punching equipment, pollutants on the surface of the grid are cleaned by using ultrasonic waves after the net punching, and meanwhile, knurling is added on the surface of the grid, namely, rough treatment is performed.
The positive active material comprises the following components in percentage by mass: 0.08% of acrylic staple fiber, 0.4% of activated carbon, 3% of tetrabasic lead sulfate, 10% of red lead, 0.1% of antimony trioxide, 0.05% of titanium dioxide, 0.2% of stannous sulfate, 0.5% of porous glass micro-beads, 10% of distilled water, 1.450g/ml of dilute sulfuric acid, and the balance of lead powder with the oxidation degree of 72-85%.
The preparation process of the positive active material comprises the following steps: putting the lead powder, acrylic staple fiber, activated carbon, tetrabasic lead sulfate, red lead, antimony trioxide, titanium dioxide, stannous sulfate and porous glass beads in a formula amount into a vacuum paste mixing machine for dry stirring for 2-5 min, then quickly adding distilled water in the formula amount, continuously stirring for 3-5 min, adding dilute sulfuric acid in the formula amount of 1.450g/ml for 4 times, controlling the vacuum degree in the process, controlling the reaction to be kept for 5min at the temperature of 75-80 ℃ by utilizing the heat generated by the reaction of the sulfuric acid and the lead oxide, finally stirring for 3-5 min, testing the apparent specific gravity of 4.3-4.6 g/cm3, and mixing the paste.
The vacuum degree in the four times of dilute sulfuric acid addition processes is sequentially controlled as follows: 380mbar, 330mbar, 280mbar and 260 mbar.
The preparation method of the deep cycle power battery positive plate comprises the following steps of filling the prepared positive active substance on a positive grid by adopting continuous plate coating equipment according to the standard of 380 +/-5 g, stacking 15-20 positive grids, and conveying the positive grids into a high-temperature curing chamber for curing, wherein the curing process is as follows:
and after solidification, testing that the water content in the active substance of the positive plate is less than or equal to 0.5 percent, the free lead content is less than or equal to 8 percent, and finishing the preparation of the positive plate.
The finished battery product internalized by the positive plate of the embodiment has the highest capacity of 226 Ah for three times, the discharge capacity of 3.6C3 is 196 min, and the 100 percent DOD cycle life is 675 times; the maximum three-time capacity of the conventional battery is 212 Ah, the 3.6C3 discharge capacity is 162min, and the 100 percent DOD cycle life is 432 times. Dissecting the battery internalized by the positive plate of the embodiment after the service life is ended, wherein the positive plate grid is intact, and the positive active substance falls off normally; the positive grid of the conventional battery is seriously corroded, the ribs are brittle and broken, and the positive active substances are completely argillized after being blocked and falling off.
Example 2
The positive grid is made of a lead-calcium-tin-silver-selenium-lanthanum aluminum alloy material, and the positive grid comprises the following components in percentage by weight: 0.05% of calcium, 1.5% of tin, 0.001% of silver, 0.08% of selenium, 0.02% of lanthanum and 0.05% of aluminum.
The positive active material comprises the following components in percentage by mass: 0.07 percent of acrylic staple fiber, 0.6 percent of active carbon, 1 percent of tetrabasic lead sulfate, 15 percent of red lead, 0.2 percent of antimony trioxide, 0.08 percent of titanium dioxide, 0.08 percent of stannous sulfate, 1 percent of porous glass micro-bead, 15 percent of distilled water, 10 percent of 1.450g/ml dilute sulfuric acid and the balance of lead powder with the oxidation degree of 72-85 percent.
The preparation process of the positive electrode active material and the positive grid and the structure of the positive grid are the same as those of example 1.
The finished battery product internalized by the positive plate of the embodiment has the highest three-time capacity of 228Ah, 3.6C3 discharge capacity of 195min and 100% DOD cycle life of 623 times through detection; the maximum three-time capacity of the conventional battery is 212 Ah, the 3.6C3 discharge capacity is 162min, and the 100 percent DOD cycle life is 432 times. Dissecting the battery internalized by the positive plate of the embodiment after the service life is ended, wherein the positive plate grid is intact, and the positive active substance falls off normally; the positive grid of the conventional battery is seriously corroded, the ribs are brittle and broken, and the positive active substances are completely argillized after being blocked and falling off.
Example 3
The positive grid is made of a lead-calcium-tin-silver-selenium-lanthanum aluminum alloy material, and the positive grid comprises the following components in percentage by weight: 0.10% of calcium, 0.8% of tin, 0.004% of silver, 0.10% of selenium, 0.08% of lanthanum and 0.03% of aluminum.
The positive active material comprises the following components in percentage by mass: 0.15 percent of acrylic staple fiber, 0.3 percent of active carbon, 5 percent of tetrabasic lead sulfate, 5 percent of red lead, 0.2 percent of antimony trioxide, 0.1 percent of titanium dioxide, 0.10 percent of stannous sulfate, 0.3 percent of porous glass micro-bead, 12 percent of distilled water, 8 percent of dilute sulfuric acid with the concentration of 1.450g/ml and the balance of lead powder with the oxidation degree of 72-85 percent.
The preparation process of the positive electrode active material and the positive grid and the structure of the positive grid are the same as those of example 1.
In the finished battery product internalized by the positive plate, the detection shows that the maximum capacity of the battery product internalized by the positive plate is 227Ah, the 3.6C3 discharge capacity is 197min, and the 100% DOD cycle life is 715 times; the maximum three-time capacity of the conventional battery is 212 Ah, the 3.6C3 discharge capacity is 162min, and the 100 percent DOD cycle life is 432 times. Dissecting the battery internalized by the positive plate of the embodiment after the service life is ended, wherein the positive plate grid is intact, and the positive active substance falls off normally; the positive grid of the conventional battery is seriously corroded, the ribs are brittle and broken, and the positive active substances are completely argillized after being blocked and falling off.
Claims (8)
1. The deep-cycle power battery positive plate comprises a positive plate grid and a positive active substance, and is characterized in that the structure of the positive plate grid adopts a radiation type structural design, the specific structure of the positive plate grid comprises a frame (4), a lug (1) arranged on the frame (4), a main diagonal rib (2) arranged in the frame (4), a sub diagonal rib (3) and a transverse rib (5), and the main diagonal ribs (2) which are separated in pairs are radiated to form the sub diagonal ribs (3) in a mode of dividing one into two within the interval range of the two transverse ribs (5) on the middle position of the frame (4).
2. The deep cycle power battery positive plate according to claim 1, wherein the upper and lower surfaces of the frame (4), the main tilted rib (2), the sub tilted rib (3) and the transverse rib (5) are provided with knurls (6).
3. The deep cycle power battery positive plate of claim 1, wherein the positive plate grid is made of a lead-calcium-tin-silver-selenium-lanthanum aluminum alloy, and the positive plate grid comprises the following components in percentage by weight: 0.05-0.10% of calcium, 0.8-1.5% of tin, 0.001-0.004% of silver, 0.02-0.10% of selenium, 0.02-0.08% of lanthanum, 0.03-0.05% of aluminum and the balance of lead.
4. The deep cycle power battery positive plate according to claim 3, characterized in that the positive plate grid is manufactured by adopting a belt manufacturing and net punching preparation process, firstly, a lead-calcium-tin-silver-selenium-lanthanum-aluminum alloy is melted, a lead belt with the width of 380mm and the thickness of 0.8mm is prepared through multi-stage rolling, then, a grid is prepared by using net punching equipment, pollutants on the surface of the grid are cleaned by using ultrasonic waves after the net punching, meanwhile, knurling (6) is added on the surface of the grid, and the knurling (6) is subjected to rough treatment.
5. The deep cycle power battery positive plate of claim 1, wherein the positive active material comprises, in mass percent: lead powder with the oxidation degree of 72-85%, acrylic staple fiber 0.07-0.15%, active carbon 0.3-0.6%, tetrabasic lead sulfate 1-5%, red lead 5-15%, antimony trioxide 0.08-0.2%, titanium dioxide 0.05-0.1%, stannous sulfate 0.08-0.2%, porous glass micro-beads 0.3-1%, distilled water 10-15%, and dilute sulfuric acid 8-10% with the density of 1.450 g/ml.
6. The deep cycle power cell positive plate of claim 5, wherein: the preparation process of the positive active material comprises the following steps: putting the lead powder, acrylic staple fiber, activated carbon, tetrabasic lead sulfate, red lead, antimony trioxide, titanium dioxide, stannous sulfate and porous glass beads in a formula amount into a vacuum paste mixing machine for dry stirring for 2-5 min, then quickly adding distilled water in the formula amount, continuously stirring for 3-5 min, adding dilute sulfuric acid in the formula amount of 1.450g/ml for 4 times, controlling the vacuum degree in the process, controlling the reaction to be kept for 5min at the temperature of 75-80 ℃ by utilizing the heat generated by the reaction of the sulfuric acid and the lead oxide, finally stirring for 3-5 min, testing the apparent specific gravity of 4.3-4.6 g/cm3, and mixing the paste.
7. The deep cycle power cell positive plate of claim 6, wherein: the vacuum degree in the four times of dilute sulfuric acid addition processes is sequentially controlled as follows: 380mbar, 330mbar, 280mbar and 260 mbar.
8. A method for preparing a positive plate of a deep cycle power battery, wherein the positive active material prepared according to claim 6 is filled on a positive plate grid according to the standard of 380 +/-5 g by using continuous plate coating equipment, the positive plate grid is put according to 15-20 pieces/stack and sent into a high-temperature curing chamber for curing, and the curing process is as follows: the first stage, curing for 1 hour in an environment with 55 ℃ and 99% of humidity; in the second stage, curing is carried out for 8 hours in an environment with the temperature of 55 ℃ and the humidity of 99 percent; a third stage, curing for 1 hour at 75 ℃ and in an environment with the humidity of 99 percent; a fourth stage, curing for 8 hours in an environment with 75 ℃ and 99% of humidity; a fifth stage, curing for 2 hours in an environment with the temperature of 57 ℃ and the humidity of 99 percent; a sixth stage of curing at 57 ℃ for 1 hour in an environment with a humidity of 95%; a seventh stage of curing for 4 hours at 57 ℃ in an environment with a humidity of 95%; an eighth stage, curing for 1 hour at 57 ℃ and in an environment with a humidity of 90%; ninth, curing for 4 hours at 57 ℃ and 90% humidity; in the tenth stage, curing is carried out for 2 hours in an environment with the temperature of 57 ℃ and the humidity of 80 percent; an eleventh stage, curing for 6 hours at 57 ℃ and 60% humidity; a twelfth stage of drying at 57 ℃ for 4 hours at a humidity of 25%; a thirteenth stage of drying at 65 ℃ for 3 hours at a humidity of 25%; a fourteenth stage of drying at 70 ℃ for 1 hour at a humidity of 25%; a fifteenth step of drying the mixture at 75 ℃ for 1 hour at a humidity of 0%; sixteenth stage, drying for 8 hours at 75 ℃ and 0% humidity; seventeenth stage, drying for 2 hours at 75 deg.C and 0% humidity; and after solidification, testing that the water content in the active substance of the positive plate is less than or equal to 0.5 percent, the free lead content is less than or equal to 8 percent, and finishing the preparation of the positive plate.
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| CN202010104272.1A CN111261839A (en) | 2020-02-20 | 2020-02-20 | Deep-cycle power battery positive plate and preparation method thereof |
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Application publication date: 20200609 |