WO2016006080A1 - 鉛蓄電池用極板の製造方法 - Google Patents
鉛蓄電池用極板の製造方法 Download PDFInfo
- Publication number
- WO2016006080A1 WO2016006080A1 PCT/JP2014/068445 JP2014068445W WO2016006080A1 WO 2016006080 A1 WO2016006080 A1 WO 2016006080A1 JP 2014068445 W JP2014068445 W JP 2014068445W WO 2016006080 A1 WO2016006080 A1 WO 2016006080A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode plate
- sulfuric acid
- active material
- filled
- press
- Prior art date
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
- H01M10/12—Construction or manufacture
-
- 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
Definitions
- the present invention relates to a method for producing an electrode plate for a lead storage battery, and more particularly to a method for producing an unformed electrode plate by filling a lattice substrate with a paste-like active material.
- a paste-type electrode plate for a lead-acid battery is prepared by filling a grid substrate made of a lead alloy with a paste-like active material, aging and drying.
- Patent Document 1 in the production of a positive electrode plate for a lead storage battery, a paste-like active material added with red lead is filled in a lattice substrate, and then the surface of the positive electrode plate has a concentration of 10% by mass.
- the manufacturing method of the electrode plate which suppresses the fall of cycling characteristics by maintaining the utilization factor of a positive electrode active material by making it react with 60 mass% or less sulfuric acid and lead-izing is disclosed.
- Patent Document 2 an electrode plate filled with an active material in a lattice substrate is passed through a pair of soaking rolls containing dilute sulfuric acid on the surface, so that an electrode is formed in the next drying step.
- a method for manufacturing an electrode plate for a lead storage battery that prevents cracks on the surface of the plate is disclosed.
- An object of the present invention is to provide a method for producing a lead-acid battery electrode plate that can prevent the surface of the electrode plate from being cracked or cracked.
- Another object of the present invention is to provide a method for producing a lead-acid battery electrode plate in which the electrode plates are less likely to stick during manufacturing.
- Still another object of the present invention is to provide a method for manufacturing an electrode plate that can increase the initial capacity of a lead-acid battery.
- the method for producing a lead-acid battery electrode plate to be improved by the present invention includes an active material filling step, a press molding step, and an aging / drying step.
- an active material-filled electrode plate is produced by filling a paste alloy material into a lead alloy lattice substrate.
- the active material-filled electrode plate means an electrode plate before aging and drying, compared to an unformed electrode plate after aging and drying described later.
- the active material filled electrode plate produced in the active material filling process is press molded.
- the method of press molding is arbitrary, press molding becomes easy by using a roll press machine described later.
- the aging / drying step is a step in which the active material-filled electrode plate press-formed in the press-forming step is aged and dried to form an unformed electrode plate.
- the unformed electrode plate that has been aged and dried is then subjected to a chemical conversion treatment to become an electrode plate for a lead storage battery.
- the production method of the present invention further includes a sulfuric acid treatment step and a preheating step.
- the sulfuric acid treatment step the surface of the active material filled electrode plate produced in the active material filling step is treated with sulfuric acid adjusted to a temperature higher than room temperature.
- the paste-like active material filled in the lattice substrate reacts with sulfuric acid to produce lead sulfate crystals.
- room temperature means 25 ° C.
- the method for the sulfuric acid treatment is arbitrary, and any method may be adopted as long as it can form lead sulfate crystals on the surface of the active material-filled electrode plate.
- the period during which the sulfuric acid treatment process is performed may be any period from after the active material filling process to before the press molding process, during the press molding process, and after the pressing process until before the preliminary drying process described later. .
- the pre-drying step is a step of pre-drying the active material-filled electrode plate treated with sulfuric acid in the sulfuric acid treatment step.
- This preliminary drying is a preliminary drying performed before the active material-filled electrode plate is aged in a subsequent aging / drying step, and is sometimes referred to as primary drying with respect to the drying after the aging.
- Pre-drying (primary drying) is a process performed to remove excess moisture on the surface of the active material and to grow a lead sulfate crystal formed by a chemical reaction between sulfuric acid and the active material to form an appropriate lead sulfate layer. Yes, drying furnace temperature control, drying time and drying method are important.
- the pre-drying temperature is too high, the water in the paste-like active material is excessively evaporated, and the chemical reaction in the subsequent aging / drying process is hindered.
- the temperature of the preliminary drying is too low, it takes time to obtain an appropriate drying state, and the production efficiency decreases.
- the preliminary drying is performed by heating the inside of the drying furnace. Heating in the drying furnace is performed by an electric heater or hot air. If an electric heater is used, the temperature of the paste-like active material filled in the electrode plate rises rapidly, so that the moisture content of the paste-like active material is appropriately maintained and an appropriate lead sulfate layer is formed. It is difficult to adjust the temperature in the drying furnace.
- the surface of the active material is also dried by the wind, so that the moisture content in the paste-like active material can be maintained at a specified amount even if the temperature of the warm air is set low. it can. Therefore, it is relatively easy to form a lead sulfate layer on the surface of the active material by drying using hot air, and to remove moisture on the surface of the active material to such an extent that the active material on the surface does not fall off.
- the production method of the present invention it is possible to prevent cracks and cracks from occurring on the surface of the unformed electrode plate.
- preliminary drying primary drying
- the active material-filled electrode plates are aligned so as to face each other during the ripening / drying step, the surfaces of the adjacent active material-filled electrode plates come into contact with each other, making it difficult for the active materials to stick to each other.
- the active materials are attached to each other, it is possible to prevent the active materials from falling off when the active materials attached to each other are separated.
- the surface of the active material-filled electrode plate is treated with sulfuric acid having a temperature higher than room temperature as in the present invention, there are seasonal fluctuations of the ambient temperature, daytime fluctuations, etc. However, it is possible to speed up the reaction between the surface of the active material-filled electrode plate (paste-like active material) and sulfuric acid. As a result, a highly crystalline lead sulfate crystal is generated on the surface of the active material-filled electrode plate, and a uniform lead sulfate layer is formed. Since the lead sulfate layer thus formed has a stronger crystal structure than the surface of the active material immediately after filling the lattice substrate, it is considered that the above effects can be obtained.
- the temperature of sulfuric acid used in the sulfuric acid treatment step is preferably adjusted to a range of 40 to 60 ° C.
- the temperature of sulfuric acid used in the sulfuric acid treatment step is preferably adjusted to a range of 40 to 60 ° C.
- the specific gravity of sulfuric acid used in the sulfuric acid treatment step is preferably adjusted to a range of 1.10 to 1.30 in terms of 20 ° C.
- the specific gravity of sulfuric acid is larger than 1.30, that is, when the concentration of sulfuric acid is high, fine lead sulfate crystals are precipitated, and the electrolyte does not easily penetrate and diffuse from the active material surface into the active material.
- the capacity of lead storage batteries tends to be small.
- the specific gravity of sulfuric acid becomes smaller than 1.10, that is, when the concentration of sulfuric acid is low, large lead sulfate crystals are precipitated and the aging reaction is difficult to proceed, so the capacity of the lead storage battery is reduced. There is a tendency.
- the sulfuric acid treatment in the sulfuric acid treatment step so that the thickness of the lead sulfate layer formed on the surface of the active material-filled electrode plate after the preliminary drying is in the range of 100 to 800 ⁇ m, It is possible to prevent cracks and cracks from forming on the surface of the chemical electrode plate, and to prevent the electrode plates from sticking when the electrode plates are overlapped.
- the sulfuric acid treatment in the sulfuric acid treatment step is preferably controlled so that the thickness of the lead sulfate layer formed on the electrode plate surface is in the range of 100 to 500 ⁇ m.
- the thickness of the lead sulfate layer is in the range of 100 to 500 ⁇ m, it is possible to prevent cracks and cracks from occurring on the surface of the unformed electrode plate, and to prevent the plates from sticking to each other when the plates are overlapped.
- the battery capacity can be maintained.
- the moisture on the surface of the electrode plate disappears when the thickness of the lead sulfate layer is 100 ⁇ m or more, it is considered that the electrodes do not adhere to each other. In other words, if the thickness of the lead sulfate layer is less than 100 ⁇ m, the amount of moisture on the surface of the electrode plate increases, the electrodes are likely to stick together, and the battery performance may be affected. Further, when the thickness of the lead sulfate layer exceeds 500 ⁇ m, the battery performance is affected, and when the thickness of the lead sulfate layer exceeds 800 ⁇ m, the influence on the battery performance may be increased (that is, if the sulfuric acid specific gravity is increased). As the lead sulfate layer becomes thicker, the battery performance may decrease).
- the sulfuric acid treatment process is preferably included in the press molding process. That is, it is preferable to simultaneously perform sulfuric acid treatment in the sulfuric acid treatment step and press molding in the press molding step.
- a roll press machine having a pair of rollers is used, and the active material filled electrode plate is press molded by passing the active material filled electrode plate between the pair of rollers.
- the press surfaces of the pair of rollers are preliminarily infiltrated with sulfuric acid used for the sulfuric acid treatment.
- sulfuric acid is applied to the surface of the active material filled electrode plate.
- the surface of the active material-filled electrode plate is simultaneously treated with sulfuric acid.
- the sulfuric acid treatment process is included in the press molding process and sulfuric acid is applied to the surface of the active material-filled electrode plate, so that the sulfuric acid treatment to the surface of the active material-filled electrode plate can be carried out without major changes to the production line. It can be done reliably.
- the sulfuric acid treatment is performed simultaneously with the press molding, a lead sulfate layer having a uniform thickness and a strong thickness can be formed on the surface of the active material-filled electrode plate. Therefore, it is possible to reliably prevent problems such as cracking of the surface of the active material-filled electrode plate during pre-drying (primary drying), and problems such as sticking between active materials during aging.
- the surface of the active material-filled electrode plate is treated with sulfuric acid adjusted to a temperature higher than room temperature, it is possible to prevent the electrode plate surface from being cracked or cracked.
- the active materials are not separated when the active materials are separated from each other. It can be prevented from falling off.
- FIG. 1 A graph showing the relationship between the specific gravity of sulfuric acid used for the sulfuric acid treatment (immersion sulfuric acid specific gravity) and the thickness of the lead sulfate layer formed on the surface of the active material-filled electrode plate by sulfuric acid treatment (sulfuric acid penetration / acid immersion layer thickness) is there.
- (A) to (C) are photographs of a cross section near the surface of an active material-filled electrode plate treated with sulfuric acid having a specific gravity of 1.10 to 1.30, magnified 100 times using an optical digital metal microscope. It is the microscope picture which was done.
- FIG. 1 shows a manufacturing process of an electrode plate for a lead storage battery showing an example of the present invention.
- the lattice substrate 3 is mounted on the belt conveyor 1.
- a cast lattice substrate or an expanded lattice substrate can be used.
- the material of the lattice substrate the main raw material is lead, and tin, calcium, antimony and the like can be added.
- a lattice substrate made of lead alloy to which calcium and tin were added was used. This is because, when calcium is added, the rate of self-discharge can be reduced, and the addition of tin can suppress the susceptibility of electrode plate corrosion, which is a problem when adding calcium. It is.
- the active material filling electrode plate 7 is manufactured by filling the lattice substrate 3 mounted on the belt conveyor 1 with the active material using the filling machine 5 (active material filling step).
- active material a paste-like material is used so that the lattice substrate 3 can be easily filled.
- the composition of the paste-like active material is not particularly limited, but lead powder containing lead monoxide, water, sulfuric acid, etc. (cut fiber, carbon powder, lignin, barium sulfate according to the characteristics of the positive electrode and negative electrode) In some cases, additives such as red lead may be added).
- the amount of the paste-like active material filled in the lattice substrate is an amount that can at least completely cover the lattice of the lattice substrate 3, but preferably the thickness of the frame bone that is the outermost peripheral portion of the lattice substrate 3 The amount that can be filled up to.
- the active material-filled electrode plate 7 prepared by filling the lattice substrate 3 with a paste-like active material is molded by press molding (press molding process).
- a roll press machine 9 including a pair of rollers 9A and 9B is used.
- the active material-filled electrode plate 7 is passed through a gap between a pair of rollers 9A and 9B of a pair of roll press machines 9 to perform press molding.
- the pair of rollers 9A and 9B may be composed of at least one roller, but in this example, the pair of rollers 9A and 9B is shown in FIG. 1 so that the paste-like active material can be sufficiently pressed and filled. Three rollers were each arranged as shown.
- the surface of the active material-filled electrode plate 7 is further treated with sulfuric acid adjusted to a temperature higher than room temperature (sulfuric acid treatment step).
- Sulfuric acid is stored in a sulfuric acid tank 11 made of a resin such as polypropylene and polyethylene having chemical resistance, or coated with resin, metal, etc. with a fluororesin.
- the sulfuric acid in the sulfuric acid tank 11 is heated to a set temperature by the heating device 13.
- the heating device 13 is composed of a quartz glass heater, and the quartz glass heater is immersed in the sulfuric acid tank 11 to heat the sulfuric acid, and a temperature signal measured using a K thermocouple coated with a fluorine resin (not shown) is shown. Not transmitted to the temperature controller to control the temperature of the quartz glass heater.
- the capacity of the sulfuric acid tank 11 is 2 m 3
- the heater capacity 2 kW ⁇ 3 quartz glass heaters 13 are used.
- sulfuric acid is heated to a temperature higher than room temperature in this way.
- the specific gravity of sulfuric acid is measured using a specific gravity measuring instrument (not shown), and an open / close valve of a reserve tank (not shown) of concentrated sulfuric acid and pure water connected to the sulfuric acid tank 11 is controlled. Holds specific gravity.
- the sulfuric acid treatment process is included in the press molding process. That is, the sulfuric acid treatment process for treating the surface of the active material filled electrode plate 7 with sulfuric acid is performed together with the press molding process for press molding the active material filled electrode plate 7.
- sulfuric acid having a temperature higher than room temperature used for the sulfuric acid treatment is infiltrated into the press surfaces of the pair of rollers in advance.
- sulfuric acid pumped up from the sulfuric acid tank 11 by an acid-resistant pump (not shown) is transferred using a tube 14 and dropped onto the press surface of the roll press machine 9 (a pair of rollers 9A and 9B). Infiltrate with sulfuric acid.
- a structure in which the press surfaces are covered with a cloth may be used, and when a sufficient amount of sulfuric acid is retained, a porous material or the like may be used. good.
- fluororubber a porous body using an ultra-high molecular polyethylene material, a sintered porous body of a fluororesin, and the like can be used. In this example, it was set as the structure which covered the surrounding surface of each of a pair of roller arrange
- the pump is provided with a control means for adjusting the flow rate of sulfuric acid, and the discharge amount can be adjusted as appropriate.
- the discharge amount is controlled so as to be variable in a range of 1 to 10 dm 3 / min by a controller (not shown).
- the discharge rate is set to 5 dm 3 / min using an acid-resistant self-priming pump.
- the sulfuric acid specific gravity is controlled to be within the set range.
- the amount of sulfuric acid in the sulfuric acid tank 11 is controlled within a set range by a liquid level meter (not shown).
- the active material-filled electrode plate 7 is placed in a state where sulfuric acid is dropped on the press surfaces of the roll press machine 9 (the pair of rollers 9A and 9B) and the press surfaces of the pair of rollers 9A and 9B are infiltrated with sulfuric acid.
- sulfuric acid infiltrated into the press surface is applied to the surface of the active material-filled electrode plate 7 simultaneously with the press forming of the active material-filled electrode plate 7.
- sulfuric acid dripped onto the press surface of the roll press machine 9 (a pair of rollers 9A, 9B), sulfuric acid that was not applied to the surface of the active material-filled electrode plate 7 (the sulfuric acid that was not infiltrated into the pair of rollers 9A, 9B was removed). Is dropped into the sulfuric acid recovery tank 15 and recovered, and is sent to the sulfuric acid tank 11 through the tube 16 by an acid-resistant self-priming pump capable of adjusting the discharge amount (not shown).
- the sulfuric acid recovery tank 15 may be provided in the sulfuric acid recovery tank 15 to remove these muddy substances. Further, since the sludge in the sulfuric acid has a large specific gravity and precipitates at the bottom of the sulfuric acid tank 11, the sulfuric acid may be pumped from near the liquid surface of the sulfuric acid tank 11 and supplied to the roll press machine 9.
- the active material-filled electrode plate 7 that has been subjected to press molding and sulfuric acid treatment is subjected to preliminary drying before aging and drying (preliminary drying step).
- a predrying furnace 17 provided on a belt conveyor 2 adjacent to the belt conveyor 1.
- a circulation type hot air drying furnace in which the temperature in the furnace is adjusted to 100 to 150 ° C. is used as the preliminary drying furnace 17, the drying time is set to 15 to 25 seconds, and the moisture content of the pasty active material was adjusted to 8 to 11% by mass.
- the active material-filled electrode plate 7 that has been pre-dried is aged and dried under the predetermined conditions described later (aging / drying step) to become an unformed electrode plate.
- the amount of water added was adjusted so that the paste-like active material had a certain hardness in consideration of the filling properties of the paste-like active material into the lattice substrate.
- the positive electrode paste-like active material produced by the above-described method was filled into the lattice substrate 3 to produce an unformed paste-type positive electrode plate 7. That is, a lead-calcium alloy cast lattice substrate having a lattice shape of length: 240 mm, width: 140 mm, and thickness: 4.3 mm is filled with a positive electrode paste active material so that the electrode plate thickness is 4.4 mm. To do. Thereafter, the active material-filled electrode plate 7 is passed between the pair of rollers 9A and 9B in a state where sulfuric acid whose temperature and specific gravity are set to predetermined values is always dripped onto the press surface of the roll press machine (a pair of rollers). Subsequently, drying is performed for 20 seconds in a circulating hot air drying furnace (preliminary drying furnace) 17 adjusted to 130 ° C., and preliminary drying (primary drying) is performed.
- a circulating hot air drying furnace preliminary drying furnace 17 adjusted to 130 ° C.
- the amount of water added was adjusted so that the paste-like active material had a certain hardness in consideration of the filling properties of the paste-like active material into the lattice substrate.
- the paste-form active material for negative electrode produced by the above-mentioned method was filled in a lattice substrate to produce an unchemical pasted negative electrode plate. That is, a lead-calcium alloy cast lattice substrate having a grid shape of length: 240 mm, width: 140 mm, and thickness: 2.5 mm is filled with a paste active material for negative electrode so that the thickness of the electrode plate is 2.6 mm. To do.
- the active material-filled electrode plate is passed between rollers in which sulfuric acid whose temperature and specific gravity are set to predetermined values is constantly dripped onto the press surface, and then, in a circulating hot air drying furnace adjusted to 130 ° C., 20 Dry for 2 seconds and perform preliminary drying (primary drying).
- Example 1 after applying sulfuric acid to the surface of the electrode plate, preliminary drying (primary drying), aging and drying are performed under the same conditions.
- the sulfuric acid temperature is higher than 25 ° C. (Examples 1 to 5)
- the sulfuric acid temperature is 25 ° C. or lower (Comparative Example 1)
- the lead sulfate crystal is obtained when the preliminary drying (primary drying) step is completed. It is considered that sticking of the electrode plate did not occur because the density and lead sulfate layer were appropriately formed.
- the sulfuric acid temperature is 25 ° C. or lower, it is necessary to grow the lead sulfate crystal by increasing the preliminary drying (primary drying) temperature and extending the drying time.
- pre-drying When the sulfuric acid temperature is higher than 25 ° C., pre-drying (primary drying) can be completed in a shorter time than when the sulfuric acid temperature is lower than 25 ° C., and energy for maintaining the temperature of the pre-drying (primary drying) furnace Can be reduced.
- Example 6 to 9 An unformed electrode plate was manufactured through the same steps as in Example 1 except that the temperature and specific gravity of sulfuric acid dropped on the peripheral surface of the roller were changed as shown in Table 2. The presence or absence of sticking of the manufactured electrode plates and the battery capacity of a lead storage battery assembled using these electrode plates were confirmed.
- Electrode plates produced in Examples 1 and 6 to 9 were subjected to a 0.1 CA discharge test under test conditions based on JIS standard JIS C 8704-2-1, and a low rate discharge capacity was confirmed.
- Table 2 shows the discharge time until the end voltage is reached, together with the presence or absence of sticking between the electrode plates.
- the specific gravity of the electrodes is 1.10 to 1. It is most preferable to apply sulfuric acid at a temperature of 30 to 40 ° C.
- Example 10 to 14 and Comparative Examples 2 to 5 As the sulfuric acid treatment of the active material-filled electrode plate, the surface of the active material-filled electrode plate that has been press-formed before the sulfuric acid treatment is immersed in sulfuric acid whose temperature and specific gravity are changed as shown in Table 3 described later Thus, a lead sulfate layer was formed on the surface of the active material-filled electrode plate. Otherwise, the unformed electrode plate was manufactured through the same steps as in Example 1. In this example, after confirming the thickness of the lead sulfate layer on the surface of the electrode plate against the specific gravity of sulfuric acid, the presence or absence of sticking of the manufactured electrode plates and the battery capacity of the lead storage battery assembled using these electrode plates are confirmed. did.
- the presence or absence of sticking of the manufactured electrode plates was evaluated in the same manner as in the evaluation test 1 described above. Further, the battery capacity was confirmed as a low rate discharge capacity as in the evaluation test 3 described above.
- the thickness of the lead sulfate layer on the surface of the electrode plate changes depending on the specific gravity of sulfuric acid used for the sulfuric acid treatment. Further, from FIG. 2, FIG. 3 and Table 3, no sticking between the electrodes was observed when the thickness of the lead sulfate layer on the surface of the electrodes was in the range of 100 to 800 ⁇ m (0.1 to 0.8 mm) ( Examples 10 to 14). In particular, when the thickness of the lead sulfate layer on the surface of the electrode plate is in the range of 100 to 500 ⁇ m (0.1 to 0.5 mm), it has been found that the electrodes do not stick together and a good discharge time can be obtained. (Examples 10 to 12).
- the results of Examples 10 to 14 and Comparative Examples 2 to 5 indicate that the sulfuric acid treatment is controlled so that the thickness of the lead sulfate layer formed on the surface of the electrode plate after the preliminary drying is in the range of 100 to 800 ⁇ m. By doing this, it is shown that sticking of electrode plates can be prevented. Furthermore, by controlling the sulfuric acid treatment so that the thickness of the lead sulfate layer formed on the surface of the electrode plate after preliminary drying is in the range of 100 to 500 ⁇ m (see FIG. 3), the battery characteristics are maintained while maintaining the battery characteristics. This shows that the sticking between the plates can be prevented.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
一酸化鉛を主成分とする鉛粉:1000kgと、PET繊維[繊度:2.0D(denier)、繊維長:3.0mm]:2kgを混合し、水を加えた後、希硫酸:200kg(比重:1.260、20℃換算)に、鉛丹:300kgを加えて攪拌したスラリーを加えて混練し、正極用のペースト状活物質を作製した。
上述の方法で作製した正極用ペースト状活物質を格子基板3に充填して、未化成のペースト式正極板7を作製した。即ち、縦:240mm、横:140mm、厚み:4.3mmの格子形状をした鉛-カルシウム合金製の鋳造格子基板に、正極用ペースト状活物質を極板厚みが4.4mmになるように充填する。その後、温度、比重を所定値に設定した硫酸が常にロールプレス機(一対のローラ)のプレス面に滴下された状態で、一対のローラ9A,9B間に活物質充填極板7を通過させる。続いて、130℃に調整された循環式の熱風乾燥炉(予備乾燥炉)17内で20秒間乾燥させ、予備乾燥(一次乾燥)を行う。
(二次放置):雰囲気温度50~65℃、相対湿度50%以上、20時間以上
(乾燥) :55~65℃ 24時間以上
<負極用ペースト状活物質の作製>
一酸化鉛を主成分とする鉛粉:900kgと、PET繊維[繊度:2.0D(denier)、繊維長:3.0mm]:2.7kgと、硫酸バリウム:4.5kgと、リグニン:1.8kgとを混合し、水を加えた後、希硫酸:100kgを加え混練し、負極用のペースト状活物質を作製した。
上述の方法で作製した負極用ペースト状活物質を格子基板に充填して、未化成のペースト式負極板を作製した。即ち、縦:240mm、横:140mm、厚み:2.5mmの格子形状をした鉛-カルシウム合金製の鋳造格子基板に、負極用ペースト状活物質を極板厚みが2.6mmになるように充填する。その後、温度、比重を所定値に設定した硫酸がプレス面に常に滴下されているローラ間に活物質充填極板を通過させ、続いて130℃に調整された循環式の熱風乾燥炉内で20秒間乾燥させ、予備乾燥(一次乾燥)を行う。
(二次放置):雰囲気温度37~43℃、相対湿度50%以上、16時間以上
(乾燥) :35~45℃ 8時間、65~75℃ 12時間
[実施例1~5、比較例1]
ローラのプレス面に滴下する硫酸の温度と比重を表1に示すように変化させて、上記正極板と負極板の表面に硫酸を塗布し、続いて予備乾燥(一次乾燥)、熟成、乾燥した未化成極板について、極板どうしの貼り付きの有無と、これらの未化成極板を用いて組み立てた鉛蓄電池の初期容量を確認した。
実施例1~5、比較例1の条件で作製した未化成極板について、熟成、乾燥後の極板どうしの貼り付きの有無を確認した。貼り付きの有無は、予備乾燥(一次乾燥)後の活物質充填極板を、極板どうしが重なるように積層し、荷重をかけることなく2時間放置し、その後、手で上側の極板を持ち上げる際に、下側の極板が僅かでも密着して持ち上がった場合を貼り付き有「×」とし、その他の場合を「○」とした。本試験の結果を表1に併せて示す。
実施例1~5により作製した極板を用いて鉛蓄電池を組み立て、JIS規格JIS C 8704-2-1に基づく試験条件で1.0CA放電試験を行い、高率放電容量を確認した。終止電圧に達するまでの放電時間を表1に併せて示す。
ローラ周面に滴下する硫酸の温度と比重を表2に示すように変化させて、そのほかは実施例1と同様の工程を経て未化成極板を製造した。製造した極板どうしの貼り付きの有無と、これら極板を用いて組み立てた鉛蓄電池の電池容量を確認した。
実施例1、6~9により作製した極板について、JIS規格JIS C 8704-2-1に基づいた試験条件で0.1CA放電試験を行い、低率放電容量を確認した。終止電圧に達するまでの放電時間を、極板どうしの貼り付きの有無とともに表2に示す。
活物質充填極板の硫酸処理として、硫酸処理を行う前にプレス成形を行った活物質充填極板の表面を、後述する表3に示すように温度と比重を変化させた硫酸に浸漬することにより、活物質充填極板の表面に硫酸鉛層を形成した。その他は実施例1と同様の工程を経て未化成極板を製造した。この例では、硫酸の比重に対する極板表面の硫酸鉛層の厚みを確認した上で、製造した極板どうしの貼り付きの有無と、これら極板を用いて組み立てた鉛蓄電池の電池容量を確認した。
実施例10~14及び比較例2~5により作製した極板について、極板の断面を光学式デジタル金属顕微鏡(株式会社ナカデンインターナショナル製、MX-1200II、100倍)で観察し、観察した状態を確認した。確認した極板の表面付近の状態から、硫酸処理に用いた硫酸の比重(浸漬に用いた硫酸の比重)と極板表面に形成された硫酸鉛層の厚み(硫酸の侵入による酸浸層の厚さ)との関係を確認した。その結果を、対応する硫酸比重とともに図2、図3及び表3に示す。
3 格子基板
5 充填機
7 活物質充填極板
9 ロールプレス機
9A,9B ローラ
11 硫酸槽
13 加熱装置(石英ガラスヒータ)
14,16 チューブ
15 硫酸回収槽
17 予備乾燥炉(一次乾燥炉)
Claims (9)
- 鉛合金製の格子基板にペースト状活物質を充填して活物質充填極板を作製する活物質充填工程と、
前記活物質充填極板をプレス成形するプレス成形工程と、
前記プレス成形工程でプレス成形した前記活物質充填極板を熟成、乾燥して未化成極板とする熟成・乾燥工程とを備える鉛蓄電池用極板の製造方法であって、
前記活物質充填極板の表面を、常温よりも高い温度の硫酸で処理する硫酸処理工程と、
硫酸処理工程で硫酸処理された前記活物質充填極板を、前記熟成・乾燥工程で熟成する前に予備乾燥する予備乾燥工程とをさらに備え、
前記硫酸処理工程で用いる前記硫酸は、温度が40~60℃の範囲に調整され、かつ、比重が1.10~1.30(20℃換算)の範囲に調整されており、
前記硫酸処理工程は、前記プレス成形工程に含まれており、
前記プレス成形工程では、プレス面を有する一対のローラを備えるロールプレス機を用いて、前記活物質充填極板が前記一対のローラ間を通過すると前記活物質充填極板がプレス成形され、
前記一対のローラの前記プレス面には前記硫酸が浸潤されており、前記活物質充填極板が前記一対のローラ間を通過すると、前記活物質充填極板の表面に前記硫酸が塗布されることを特徴とする鉛蓄電池用極板の製造方法。 - 鉛合金製の格子基板にペースト状活物質を充填して活物質充填極板を作製する活物質充填工程と、
前記活物質充填極板をプレス成形するプレス成形工程と、
前記プレス成形工程でプレス成形した前記活物質充填極板を熟成、乾燥して未化成極板とする熟成・乾燥工程とを含む鉛蓄電池用極板の製造方法であって、
前記活物質充填極板の表面を、常温よりも高い温度に調整された硫酸で処理する硫酸処理工程と、
硫酸処理工程で表面を硫酸処理した前記活物質充填極板を、前記熟成・乾燥工程で熟成する前に予備乾燥する予備乾燥工程とをさらに備えることを特徴とする鉛蓄電池用極板の製造方法。 - 前記硫酸処理工程で用いる硫酸の温度が、40~60℃の範囲である請求項2に記載の鉛蓄電池用極板の製造方法。
- 前記硫酸処理工程で用いる硫酸の比重が、1.10~1.30(20℃換算)の範囲である請求項2に記載の鉛蓄電池用極板の製造方法。
- 前記硫酸処理工程で用いる硫酸は、温度が40~60℃の範囲に調整され、かつ比重が1.10~1.30(20℃換算)の範囲に調整されている請求項2に記載の鉛蓄電池用極板の製造方法。
- 前記予備乾燥工程で予備乾燥した活物質充填極板の表面に形成される硫酸鉛層は、厚みが100~800μmである請求項2に記載の鉛蓄電池用極板の製造方法。
- 前記予備乾燥工程で予備乾燥した活物質充填極板の表面に形成される硫酸鉛層は、厚みが100~500μmである請求項2に記載の鉛蓄電池用極板の製造方法。
- 前記硫酸処理工程が前記プレス成形工程と同時に行われる請求項2乃至7のいずれか1項に記載の鉛蓄電池用極板の製造方法。
- 前記硫酸処理工程が前記プレス成形工程に含まれており、
前記プレス成形工程では、プレス面を有する一対のローラを備えるロールプレス機を用いて、前記活物質充填極板が前記一対のローラ間を通過すると前記活物質充填極板がプレス成形され、
前記一対のローラの前記プレス面には前記硫酸が浸潤されており、前記活物質充填極板が前記一対のローラ間を通過すると、前記活物質充填極板の表面に前記硫酸が塗布される請求項2乃至7のいずれか1項に記載の鉛蓄電池用極板の製造方法。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016532370A JP6160776B2 (ja) | 2014-07-10 | 2014-07-10 | 鉛蓄電池用極板の製造方法 |
PCT/JP2014/068445 WO2016006080A1 (ja) | 2014-07-10 | 2014-07-10 | 鉛蓄電池用極板の製造方法 |
CN201480080465.0A CN106575748B (zh) | 2014-07-10 | 2014-07-10 | 铅蓄电池用极板的制造方法 |
EP14897283.9A EP3168906B1 (en) | 2014-07-10 | 2014-07-10 | Method of manufacturing lead-acid battery electrode |
TW104122152A TWI668904B (zh) | 2014-07-10 | 2015-07-08 | 鉛蓄電池用極板的製造方法 |
TW108118130A TWI709269B (zh) | 2014-07-10 | 2015-07-08 | 鉛蓄電池用極板的製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2014/068445 WO2016006080A1 (ja) | 2014-07-10 | 2014-07-10 | 鉛蓄電池用極板の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016006080A1 true WO2016006080A1 (ja) | 2016-01-14 |
Family
ID=55063754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/068445 WO2016006080A1 (ja) | 2014-07-10 | 2014-07-10 | 鉛蓄電池用極板の製造方法 |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP3168906B1 (ja) |
JP (1) | JP6160776B2 (ja) |
CN (1) | CN106575748B (ja) |
TW (2) | TWI668904B (ja) |
WO (1) | WO2016006080A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102305183B1 (ko) * | 2020-05-20 | 2021-09-28 | 한국앤컴퍼니 주식회사 | 납축전지용 극판 표면 패터닝 방법 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109923710B (zh) * | 2016-11-08 | 2022-07-15 | 日立化成株式会社 | 铅蓄电池用活性物质材料的制造方法 |
CN108390020B (zh) * | 2018-03-28 | 2023-10-13 | 天能电池集团股份有限公司 | 一种铅蓄电池极板压制装置 |
CN108767199B (zh) * | 2018-04-19 | 2021-04-20 | 安徽力普拉斯电源技术有限公司 | 一种动力电池内化成生极板的方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6217952A (ja) * | 1985-07-16 | 1987-01-26 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用陽極板及びその製造方法 |
JPH0294257A (ja) * | 1988-09-29 | 1990-04-05 | Matsushita Electric Ind Co Ltd | 鉛蓄電池の製造方法 |
JPH04112456A (ja) * | 1990-08-31 | 1992-04-14 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JPH04181654A (ja) * | 1990-11-15 | 1992-06-29 | Yuasa Corp | 蓄電池用極板の乾燥装置 |
JPH0589875A (ja) * | 1991-09-27 | 1993-04-09 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JP2006278000A (ja) * | 2005-03-28 | 2006-10-12 | Furukawa Battery Co Ltd:The | 鉛蓄電池用極板の製造方法および鉛蓄電池 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1500254A (en) * | 1975-07-04 | 1978-02-08 | Nikolaou P | Method for the production of electrodes for lead-acid storage batteries |
JPS5220232A (en) * | 1975-08-09 | 1977-02-16 | Shin Kobe Electric Machinery | Method of producing lead battery plate |
JP2000040508A (ja) * | 1998-07-23 | 2000-02-08 | Japan Storage Battery Co Ltd | 鉛蓄電池用ペースト式極板の製造法 |
WO2008029419A2 (en) * | 2006-09-07 | 2008-03-13 | Luminous Power Technologies Pvt Ltd | Lead-acid battery plates |
TWI413288B (zh) * | 2012-03-02 | 2013-10-21 | Shin Kobe Electric Machinery | Lead battery |
-
2014
- 2014-07-10 JP JP2016532370A patent/JP6160776B2/ja active Active
- 2014-07-10 WO PCT/JP2014/068445 patent/WO2016006080A1/ja active Application Filing
- 2014-07-10 CN CN201480080465.0A patent/CN106575748B/zh active Active
- 2014-07-10 EP EP14897283.9A patent/EP3168906B1/en active Active
-
2015
- 2015-07-08 TW TW104122152A patent/TWI668904B/zh not_active IP Right Cessation
- 2015-07-08 TW TW108118130A patent/TWI709269B/zh active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6217952A (ja) * | 1985-07-16 | 1987-01-26 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用陽極板及びその製造方法 |
JPH0294257A (ja) * | 1988-09-29 | 1990-04-05 | Matsushita Electric Ind Co Ltd | 鉛蓄電池の製造方法 |
JPH04112456A (ja) * | 1990-08-31 | 1992-04-14 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JPH04181654A (ja) * | 1990-11-15 | 1992-06-29 | Yuasa Corp | 蓄電池用極板の乾燥装置 |
JPH0589875A (ja) * | 1991-09-27 | 1993-04-09 | Shin Kobe Electric Mach Co Ltd | 鉛蓄電池用極板の製造方法 |
JP2006278000A (ja) * | 2005-03-28 | 2006-10-12 | Furukawa Battery Co Ltd:The | 鉛蓄電池用極板の製造方法および鉛蓄電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3168906A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102305183B1 (ko) * | 2020-05-20 | 2021-09-28 | 한국앤컴퍼니 주식회사 | 납축전지용 극판 표면 패터닝 방법 |
Also Published As
Publication number | Publication date |
---|---|
CN106575748A (zh) | 2017-04-19 |
JP6160776B2 (ja) | 2017-07-19 |
CN106575748B (zh) | 2019-10-15 |
EP3168906A4 (en) | 2018-01-17 |
TWI668904B (zh) | 2019-08-11 |
TW201622215A (zh) | 2016-06-16 |
JPWO2016006080A1 (ja) | 2017-06-01 |
TW201937789A (zh) | 2019-09-16 |
EP3168906B1 (en) | 2019-11-20 |
TWI709269B (zh) | 2020-11-01 |
EP3168906A1 (en) | 2017-05-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6160776B2 (ja) | 鉛蓄電池用極板の製造方法 | |
RU2394308C1 (ru) | Способ и установка для непрерывного перемешивания паст для аккумуляторных пластин | |
WO2022041533A1 (zh) | 一种高耐热电解铜箔的生产方法 | |
EP2901515A1 (en) | Active material compositions comprising high surface area carbonaceous materials | |
JP2008515151A (ja) | ペースト硬化添加剤 | |
CN106663816B (zh) | 用于锂二次电池的电解铜箔及包含该电解铜箔的锂二次电池 | |
CN101345305A (zh) | 一种铅酸蓄电池生板固化干燥工艺 | |
TW201320454A (zh) | 具有被覆層之金屬箔與其製造方法、二次電池用電極及其製造方法與鋰離子二次電池 | |
CN112661199A (zh) | 一种高振实密度氧化铝包覆镁锰共掺杂四氧化三钴的制备方法 | |
US20050227149A1 (en) | Electrode | |
CN114933331A (zh) | 一种硫化物固态电解质及其制备方法 | |
US5149606A (en) | Method of treating a battery electrode with persulfate | |
JP2009037893A (ja) | 非水系二次電池用負極板の製造方法 | |
CN101412510A (zh) | 用于锂二次电池的复合石墨及其制造方法 | |
CN108110220A (zh) | 一种高负载量高压实密度锂离子电池极片制备方法 | |
JP2014127438A (ja) | 電極の製造方法及び乾燥装置 | |
JP2007220644A (ja) | 鉛蓄電池用極板の製造方法 | |
US3276975A (en) | Silver oxide electrodes | |
JP5203920B2 (ja) | 無機質成形体および焼結体 | |
WO2021033195A1 (en) | A process for preparing a composite anode for lithium ion cell | |
JP2015133197A (ja) | 二次電池用電極材料の製造方法 | |
CN108166245A (zh) | 用于制作碳纤维电池板栅的碳纤维毡处理方法 | |
KR101383054B1 (ko) | 리튬일차전지의 양극 제조방법 | |
JP2003068284A (ja) | リチウム二次電池用負極およびその製造方法、並びに、リチウム二次電池 | |
CN118136941A (zh) | 复合固体电解质薄膜及其制备方法、固态电池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14897283 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016532370 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2014897283 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014897283 Country of ref document: EP |