CN113258039B - Method for improving porosity of positive plate - Google Patents

Method for improving porosity of positive plate Download PDF

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CN113258039B
CN113258039B CN202110462734.1A CN202110462734A CN113258039B CN 113258039 B CN113258039 B CN 113258039B CN 202110462734 A CN202110462734 A CN 202110462734A CN 113258039 B CN113258039 B CN 113258039B
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plate
positive
porosity
electrode plate
licker
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CN113258039A (en
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王廷华
王静
皇甫志坤
韩二莎
祖海川
覃顺一
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Fengfan Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • H01M4/21—Drying of pasted electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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

Abstract

The method for improving the porosity of the positive plate comprises the following steps between the processes of plate coating, curing and drying: a. placing the positive electrode plate after being coated on an electrode plate conveying roller, sequentially arranging a licker-in, a spraying mechanism and a flattening roller above the electrode plate conveying roller, and distributing pricking pins on the licker-in; b. rolling the positive electrode plate by a licker-in, and extruding micropores on the positive electrode plate; c. the positive pole plate after being pressed with the holes passes through a spraying mechanism, and the spraying mechanism evenly sprays sodium bicarbonate solution with the concentration of 3% -10% onto the positive pole plate; d. and flattening the sprayed positive pole plate by a flattening roller. The invention can ensure that the sodium bicarbonate enters the inside of the green plate, so that the green plate reacts in the later curing, drying and formation stages to generate carbon dioxide gas, and a large number of air holes are formed on the surface of the green plate, thereby effectively increasing the porosity of the positive plate. Tests show that the porosity of the positive plate manufactured by the method can be obviously improved compared with the porosity of the positive plate manufactured by the conventional method, and the method is easy to implement and has good practical application value.

Description

Method for improving porosity of positive plate
Technical Field
The invention relates to a method for manufacturing a storage battery, in particular to a method for improving the porosity of a positive plate, belonging to the technical field of storage batteries.
Background
The lead-acid storage battery is a device which can be recovered after being charged and reused after chemical energy and direct-current energy are mutually converted, the process of the lead-acid storage battery is relatively mature until now, but the utilization rate of active substances is low, wherein the positive plate is particularly prominent, the utilization rate of the active substances of the positive plate is only about 55%, and the problem cannot be effectively solved in the storage battery manufacturing industry. The positive active material of lead-acid battery is lead dioxide (PbO)2) The negative active material is spongy metallic lead (Pb), the electrolyte is dilute sulfuric acid, and the reaction is as follows:
negative electrode reaction
Figure BDA0003042924680000011
Positive electrode reaction
Figure BDA0003042924680000012
The positive electrode discharge product is PbSO4Since the electrode reaction is preferentially carried out on the electrode surface, PbSO is generated4The larger molar volume blocks the pore opening of the porous electrode, so that the reactant H2SO4The non-reactive material can not be smoothly diffused to the deep part of the porous electrode, so that more non-reactive material is remained in the electrode, and the utilization rate of the positive active material is low. Therefore, increasing the porosity of the positive electrode plate can increase the positive electrode plate active material utilization rate.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a method for improving the porosity of a positive plate, which is convenient to implement and obvious in effect.
The problem of the invention is realized by the following technical scheme:
the method for improving the porosity of the positive plate comprises the steps of coating and curing and drying, wherein the following steps are arranged between the steps of coating and curing and drying:
a. placing the positive electrode plate after being coated on an electrode plate conveying roller, sequentially arranging a licker-in, a spraying mechanism and a flattening roller above the electrode plate conveying roller, and distributing pricking pins on the licker-in;
b. rolling the positive electrode plate by a licker-in, and extruding micropores on the positive electrode plate;
c. the positive pole plate after being pressed with the holes passes through a spraying mechanism, and the spraying mechanism evenly sprays sodium bicarbonate solution with the concentration of 3% -10% onto the positive pole plate;
d. and flattening the sprayed positive pole plate by a flattening roller.
According to the method for improving the porosity of the positive plate, the placing direction of the positive plate on the plate conveying roller is the same as the extending direction of the plate lug and the axial direction of the licker-in.
According to the method for improving the porosity of the positive plate, the distribution height of micropores in the height direction of the positive green plate is H1 from the upper frame and H2 from the upper frame to the lower frame, wherein H1 is more than or equal to 3H1, H2 is more than or equal to 3H2, H1 is the height of the upper frame, and H2 is the height of the lower frame.
The method for improving the porosity of the positive plate has the micropore depth of 0.5-1 mm.
According to the method for improving the porosity of the positive plate, the height of the positive green plate is H3, the width of the positive green plate is H, the size of the radius R of the puncturing needle is H3/100, R is more than or equal to H/100, or H/100, R is more than or equal to H3/100.
According to the method for improving the porosity of the positive plate, the distance L between every two adjacent rows of punching needles on the punching roller is larger than or equal to H/8, and the punching needles in the adjacent rows are staggered.
The invention improves the traditional process of adding additives in the paste mixing process of the pole plate manufacturing, adopts the method of pricking holes on the surface of a raw pole plate after coating, spraying additive solution and then flattening the raw pole plate, the additive used in the invention is sodium bicarbonate, the sodium bicarbonate is decomposed at the temperature of more than 50 ℃, the method avoids the defect that the sodium bicarbonate is decomposed to form air holes in the paste mixing process and then the air holes are greatly reduced along with the stirring of lead paste, a large amount of sprayed sodium bicarbonate solution enters the micropores, the sodium bicarbonate can be ensured to enter the raw pole plate after the surface is flattened, so that the raw pole plate can react in the subsequent curing, drying and formation stages to generate carbon dioxide gas, a large amount of air holes are formed on the surface of the raw pole plate, and the porosity of the positive pole plate is effectively increased. Tests show that compared with the conventional method, the porosity of the positive plate manufactured by the method can be obviously improved, and the method is easy to implement and has good practical application value.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is a schematic of the process of the present invention;
fig. 2 is a schematic view of the mutual position of the lickerin roll and the positive electrode plate.
The reference numbers in the figures are: 1. the plate electrode conveying device comprises a licker-in 1-1, a pricking pin 2, a spraying mechanism 3, a flattening roller 4, a positive electrode plate 4-1, an upper frame 4-2, a lower frame 4-3, plate lugs 5 and an electrode plate conveying roller.
Detailed Description
The production process of the lead-acid storage battery comprises the following steps: slab lattice, coating slab, solidifying and drying, assembling, filling acid, and forming to obtain the finished product. Referring to FIG. 1, the invention isIn the process of manufacturing the positive electrode plate, the processes of increasing pressure holes, spraying sodium bicarbonate and flattening are carried out between plate coating and curing and drying, namely: placing the positive electrode plate 4 after being coated on an electrode plate conveying roller 5, sequentially arranging a licker-in 1, a spraying mechanism 2 and a flattening roller 3 above the electrode plate conveying roller, distributing pricking pins 1-1 on the licker-in, rolling the positive electrode plate by the licker-in, and pricking micropores on the positive electrode plate; the spraying mechanism sprays sodium bicarbonate solution with the concentration of 3-10% and the temperature of less than 50 ℃ on the positive plate with the surface perforated, the sodium bicarbonate is attached to the positive plate and flows into each micropore, and then the surface of the plate is flattened. In the subsequent process of curing and drying the green plate, partial sodium bicarbonate is decomposed at high temperature to generate carbon dioxide and sodium carbonate, and the carbon dioxide is discharged from the plate to form a hole; residual sodium bicarbonate solution and H during formation of polar plate2SO4Contact, react violently to form CO2And the carbonate is expelled from the active material, enabling pore formation again. According to the method, the sodium bicarbonate is decomposed, namely reacts with sulfuric acid to generate carbon dioxide gas, the gas is discharged out of the polar plate to form holes, and the porosity of the positive polar plate is further effectively increased.
Referring to fig. 2, the positive electrode plates are placed on the electrode plate conveying rollers in such a way that the extending direction of the plate lugs 4-3 is consistent with the axial direction of the licker-in, so that the distribution of the pricking pins on the licker-in can be designed according to the height dimension H3 of the electrode plates. In order to avoid the influence of the falling of the lead paste near the frame, especially the falling of the lead paste around the plate lug on the performance of the battery at the later stage, the micropores need to be avoided around the frame as much as possible. The distribution height of the micropores in the height direction of the positive polar plate is H1 from the upper frame 4-1 and H2 from the lower frame 4-2, wherein H1 is more than or equal to 3H1, H2 is more than or equal to 3H2, H1 is the height of the upper frame, and H2 is the height of the lower frame. Namely the distribution height H of micropores is H3-H1-H2. The depth of the micropores is controlled to be 0.5-1 mm. The licker-in is supported by the mounting bracket, and the micropore depth requirement can be met by adjusting the height position of the licker-in. In order to prevent lead paste from falling off at the later stage when the diameter of the micropores is too large or the hole distance is too dense, the radius R of the punching needles is controlled to be equal to or larger than H3/100 and equal to or smaller than H/100 (H is larger than H3 in figure 1, otherwise, the radius R of the punching needles is equal to or larger than H/100 and equal to or smaller than H3/100), the distance L between every two adjacent transverse rows of the punching needles is equal to or larger than H/8, and the punching needles of the adjacent rows are distributed in a staggered manner.
Specific examples and comparative examples are given below:
the method of the invention is adopted to process the anode plate, and the size of the anode plate is as follows: h3-115 mm, H144 mm, H1-3 mm, H2-2 mm. The distribution size of micropores on the positive electrode plate is as follows: h 1-10 mm, h 2-10 mm, h 95mm, L20 mm. The radius dimension R of the puncture needle is 1.2 mm. After the positive plate is coated, the positive plate is subjected to hole pressing, spraying and flattening, then is subjected to curing, drying, assembling, acid filling and formation, and then the storage battery is dissected to determine the porosity of the six plates by a water absorption method; and then taking six positive plates with the same specification and produced according to the traditional method, dissecting the storage battery, and determining the porosity of the six positive plates in the comparative example by using the same water absorption method, wherein the detection results are shown in the following table:
Figure BDA0003042924680000041
the comparative test data show that the porosity of the plate in the embodiment is obviously higher than that in the comparative example, and the invention is proved to have good practical application value.

Claims (6)

1. The method for improving the porosity of the positive plate comprises the working procedures of plate coating and curing and drying, and is characterized in that the following steps are arranged between the working procedures of plate coating and curing and drying:
a. placing the positive electrode plate after being coated on an electrode plate conveying roller, sequentially arranging a licker-in, a spraying mechanism and a flattening roller above the electrode plate conveying roller, and distributing pricking pins on the licker-in;
b. rolling the positive electrode plate by a licker-in, and extruding micropores on the positive electrode plate;
c. the positive pole plate after being pressed with the holes passes through a spraying mechanism, and the spraying mechanism evenly sprays sodium bicarbonate solution with the concentration of 3% -10% onto the positive pole plate;
d. and flattening the sprayed positive pole plate by a flattening roller.
2. The method of increasing porosity of a positive plate of claim 1, wherein: the arrangement direction of the positive polar plate on the polar plate conveying roller is the same as the extending direction of the plate lug and the axial direction of the licker-in.
3. The method of increasing porosity of a positive plate of claim 2, wherein: the distribution height of the micropores in the height direction of the positive electrode plate is the height from the distance H1 from the upper frame (4-1) to the distance H2 from the lower frame (4-2), namely the distribution height H = H3-H1-H2 of the micropores, wherein H3 is the height of the positive electrode plate, H1 is more than or equal to 3H1, H2 is more than or equal to 3H2, H1 is the height of the upper frame, and H2 is the height of the lower frame.
4. The method of increasing porosity of a positive plate of claim 3, wherein: the depth of the micropores is 0.5-1 mm.
5. The method of increasing the porosity of a positive plate of claim 4, wherein: the height of the positive electrode plate is H3, the width of the positive electrode plate is H, the radius R of the puncturing needle is H3/100 which is more than or equal to R and less than or equal to H/100, or H/100 which is more than or equal to R and less than or equal to H3/100.
6. The method of increasing the porosity of a positive plate of claim 5, wherein: the distance L between the punching needles in adjacent rows on the punching roller is more than or equal to H/8, and the punching needles in the adjacent rows are staggered.
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US4338163A (en) * 1980-12-03 1982-07-06 Eltra Corporation Curing of tetrabasic lead pasted battery electrodes
ZA865535B (en) * 1985-07-30 1987-03-25 Polycristal Technologies Corp Porous electrodes and method of making same
US5584109A (en) * 1994-06-22 1996-12-17 Memtec America Corp. Method of making a battery plate
KR100682862B1 (en) * 2005-01-11 2007-02-15 삼성에스디아이 주식회사 Electrode for electrochemical cell, manufacturing method thereof, and electrochemical cell containing the electrode
CN210132849U (en) * 2019-06-13 2020-03-10 中国船舶重工集团衡远科技有限公司 Paper covering machine for continuous polar plate of storage battery
CN112002875A (en) * 2020-07-13 2020-11-27 天能电池集团股份有限公司 High-rate lead storage battery for communication

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