WO2013128793A1 - 電池用極板及びその製造方法、該極板を有する極板群並びに鉛蓄電池 - Google Patents

電池用極板及びその製造方法、該極板を有する極板群並びに鉛蓄電池 Download PDF

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Publication number
WO2013128793A1
WO2013128793A1 PCT/JP2013/000323 JP2013000323W WO2013128793A1 WO 2013128793 A1 WO2013128793 A1 WO 2013128793A1 JP 2013000323 W JP2013000323 W JP 2013000323W WO 2013128793 A1 WO2013128793 A1 WO 2013128793A1
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Prior art keywords
electrode plate
battery
lead
battery electrode
thickness
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PCT/JP2013/000323
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English (en)
French (fr)
Japanese (ja)
Inventor
暁申 田
宇 王
勤超 孫
道男 榑松
善博 村田
佐々木　健浩
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パナソニック株式会社
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Priority to JP2013514482A priority Critical patent/JP5325358B1/ja
Priority to IN7723DEN2014 priority patent/IN2014DN07723A/en
Publication of WO2013128793A1 publication Critical patent/WO2013128793A1/ja

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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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/22—Forming of 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an electrode plate for a battery and a method for manufacturing the same, and more specifically, a battery electrode plate having a simple process, low cost, good capacity, cycle life, and charging efficiency, and a method for manufacturing the same.
  • the present invention relates to an electrode plate group having the electrode plate and a lead storage battery.
  • Lead-acid batteries are used as main power sources in addition to power sources for vehicle start-up and backup, that is, for example, power sources such as electric cars, electric bicycles, electric motorcycles, electric scooters, moped electric motorcycles, golf carts, and solar energy. It is widely used as a power source for equipment for charging and discharging independently, such as batteries for batteries. In these applications, lead-acid batteries have operational characteristics such as a large current at start-up, a small discharge current during vehicle travel, and a long discharge time. At the same time, the lead storage battery is required to reduce maintenance, and in particular, to increase its cycle life.
  • the cross-sectional area of the positive electrode current collector is reduced, leading to a decrease in the conductivity of the positive electrode plate, As a result, the voltage characteristics when the battery performs high rate discharge deteriorates. If such corrosion of the positive electrode current collector further proceeds, the positive electrode current collector itself will eventually break. Therefore, the battery capacity is suddenly reduced and the life is exhausted.
  • the battery performance gradually decreases.
  • the internal pressure of the battery increases, and a large pressure may be applied between the positive electrode plate and the negative electrode plate.
  • the electrode group tends to be compressed or deformed. That is, the electrode group tends to be crushed as the internal pressure of the battery increases.
  • the Chinese utility model No. CN201820837U discloses a warp degree paste shielding plate for electrode plate double-side coating, and the problems to be solved are as follows. That is, the work surface at the lower end of the conventional paste blocker is flat, and when the paste is discharged, the electrode plate is depressed downward with a constant pressure by the lead paste, and the distance between the paste blocker and the center of the plate increases. However, the amount of paste applied at the center was relatively large. And the electrode plate before hardening after double-sided coating is often thick at the center and thin at both ends, and the electrode plate is significantly curved after hardening, affecting the quality of the electrode plate.
  • the above-described warpage degree paste shielding plate for double-sided application of an electrode plate includes a paste shielding plate and a paste outlet provided in the paste shielding plate for applying paste to the electrode plate, and the paste outlet is a paste
  • the arc-shaped work surface that protrudes outwardly compensates for the deformation of the electrode plate, so that the paste coating thickness of the electrode plate can be made substantially the same and the product quality can be improved. It is balanced with the board.
  • an eccentricity adjusting device for controlling the thickness of the electrode plate in the coater.
  • the eccentricity adjustment device can detect the electrode plate thickness at random during actual operation, and when the fluctuation occurs, the coater is stopped so that the thickness of the electrode plate passing through the coater becomes constant. It can be adjusted dynamically without
  • Japanese Laid-Open Patent Publication No. 57-21068 discloses a method for producing a positive electrode for a sealed lead-acid battery.
  • the manufacturing method of the positive electrode for a sealed lead-acid battery is an active material lead paste having a lead paste density of only 3.0 to 3.4 g / cm 3 (the normal lead paste density is 3.7 to 4.1 g / cm 3 ). Is packed in a lattice and dried.
  • the problem to be solved by this method is to increase the porosity of the positive electrode plate by lowering the paste density of the positive electrode plate, thereby improving the rapid discharge characteristics of the sealed lead-acid battery.
  • an aqueous dispersion of polytetrafluoroethylene is added to the lead paste in order to prevent the life from being shortened by reducing the lead paste density.
  • JP-A-58-223259 discloses a method for producing a lead-acid battery electrode plate.
  • the lead-acid battery plate is manufactured by filling a strip-shaped expanded lattice plate made of lead or a lead alloy with an active material lead paste, and then adding a cutting portion having a certain width in the longitudinal direction. It is characterized in that it is pressed and compressed, and the center of this cutting part is cut into individual plates and then dried. As shown in FIG. 4 of this document, the thickness of both end portions of the electrode plate obtained by the manufacturing method is thinner than the intermediate portion.
  • the problem to be solved by the production method is to overcome the conventional drawback that the active material has a weak holding power in the cut portion and the active material is easily dropped.
  • Japanese Unexamined Patent Application Publication No. 2007-258088 discloses an electrode plate for a lead storage battery in which an active material is filled in a grid having a current collecting ear on one end side.
  • the lattice body is formed so as to gradually increase in thickness from the one end side toward the other end side, and the active material layer extends from one end side of the lattice body to the other end.
  • the thickness of the electrode plate is the sum of the thickness of the lattice body and the thickness of the active material layer covering the lattice body. It is almost equal from one end side to the other end side.
  • the electrode plate for a lead-acid battery can prevent the active material layer in the vicinity of the ears covering the grid body from becoming too thin and part of the grid body from being exposed, thereby preventing deterioration in battery performance. be able to.
  • Japanese Unexamined Patent Application Publication No. 2003-86175 discloses a filled electrode plate for a lead storage battery having no surface unevenness and having no thickness variation.
  • the thickness of the filling electrode plate is suppressed to a uniform thickness, and the filling electrode Flatten deposits and protrusions on both sides of the plate.
  • the filled electrode plate for a lead-acid battery can prevent defects such as a short circuit more satisfactorily.
  • the electrode plate design has also been considered, and several methods have been discovered. For example, as described above, the porosity of the positive electrode plate is increased by lowering the lead paste density of the positive electrode plate, thereby improving the rapid discharge characteristics of the sealed lead-acid battery. Battery life will be shortened. Alternatively, the thickness of both end portions of the electrode plate is made thinner than that of the intermediate portion, thereby overcoming the disadvantage that the active material holding force at the end portions is weak and the active material is likely to fall off.
  • the electrode plate surface is flat and the electrode plate thickness is constant, more sulfuric acid cannot be retained and more chemical reaction cannot be performed, so it is difficult to increase the capacity. In addition, the designed initial capacity may not be achieved. In addition, if the electrode plate surface is flat and the electrode plate thickness is constant, the pitch between the positive electrode plate and the negative electrode plate becomes too small, which may cause a short circuit, affecting the cycle life. In addition, since the electrode plate is too flat and the separator and the electrode plate are in close contact with each other, the oxygen gas generated at the end of charging in the positive electrode plate cannot be immediately diffused to the negative electrode, affecting the recombination of oxygen gas. , Charging efficiency will decrease.
  • the present invention provides an electrode plate for a battery having a simple process, low cost, good capacity, cycle life and charging efficiency, a method for manufacturing the same, an electrode plate group having the electrode plate, and a lead storage battery. For the purpose.
  • the electrode plate is designed so that the end portion is formed with a protrusion to form a protruding end portion having a protrusion, and the thickness of the end portion of the electrode plate is larger than the thickness of the other portion of the electrode plate.
  • the present invention is a battery electrode plate comprising a current collector and an active material layer held by the current collector, wherein the current collector is an expanded lattice produced by an expanding method
  • the electrode plate includes two protruding end portions having protrusions and a flat intermediate portion located between the two end portions, and the thickness of the end portion is larger than the thickness of the intermediate portion,
  • the thickness of the intermediate portion is H2 and the difference between the thickness of the end portion and the thickness of the intermediate portion is H1
  • the ratio of H1 to H2 H1 / H2 is 3% to 9%.
  • the ratio H1 / H2 is preferably 4% to 8%.
  • the width of the end is preferably 5% to 25%, more preferably 10% to 20% of the entire width of the electrode plate.
  • the protrusions of each of the two protrusion-shaped end portions may be formed on the same side of the electrode plate, or may be formed on different sides of the electrode plate. Good.
  • the protrusions are preferably formed by cutting in the rotary plate method in the electrode plate cutting step, and the blade angle of the rotary cut tool used is 45 ° to 75 °. It is preferable that the angle is 50 ° to 70 °. Further, the protrusion may be formed by being cut by a punching method in the step of cutting the electrode plate.
  • density or lead paste density of the active material layer of the electrode plate is preferably 4.15g / cm 3 ⁇ 5.0g / cm 3.
  • battery plate of the present invention is preferably a positive electrode plate, the density or lead paste density of the active material layer of the positive electrode plate is 4.15g / cm 3 ⁇ 4.45g / cm 3 .
  • the present invention is a method for producing the electrode plate, wherein in the step of cutting the electrode plate, cutting is performed by a rotary cut method, and the blade angle of the rotary cut tool used in the rotary cut method is 45 °.
  • a method is further provided that is ⁇ 75 °, and the blade angle is preferably 50 ° -70 °.
  • density or lead paste density of the active material layer of the electrode plate is preferably 4.15g / cm 3 ⁇ 5.0g / cm 3.
  • the electrode plate is a positive electrode plate
  • the density or lead paste density of the active material layer of the positive electrode plate is to be 4.15g / cm 3 ⁇ 4.45g / cm 3 preferable.
  • the present invention is an electrode plate group, wherein a plurality of positive electrodes and a plurality of negative electrodes are alternately arranged via separators, and at least the positive electrode plate is the battery electrode plate of the present invention. Groups are further provided.
  • the present invention further provides a lead-acid battery, which is provided with the electrode plate group of the present invention.
  • the electrode plate is designed so that the end part is formed with a protrusion to be a protruding end part having a protrusion, and the thickness of the end part of the electrode plate is set to the thickness of the other part of the electrode plate.
  • the pitch between the positive electrode plate and the negative electrode plate is appropriately increased, thereby significantly reducing the possibility of occurrence of a short circuit, thereby improving the cycle life.
  • more electrolytic solution can be held, and more chemical reaction can be performed, thereby improving the capacity and from the positive electrode plate at the end of charging.
  • the generated oxygen gas can be immediately diffused into the negative electrode plate, which is advantageous for recombination of the oxygen gas and increases the charging efficiency.
  • Embodiment 1 of the battery electrode plate according to the present invention It is a schematic diagram of Embodiment 2 of the battery electrode plate according to the present invention.
  • A) is a perspective view which shows typically the battery electrode plate which concerns on Embodiment 1 of this invention
  • (b) is a front view of the battery electrode plate shown to (a)
  • (c) is ( It is a cross-sectional view of the battery electrode plate shown in a).
  • (A) is process drawing which shows the process of processing by an expanding method and manufacturing an expanded grating
  • (b) is a schematic diagram which expands and shows a part of said process.
  • FIG. 8 is a front view corresponding to FIG. 7.
  • the present invention provides a battery electrode plate, the battery electrode plate comprising a current collector and an active material layer held by the current collector, wherein the current collector is an expanded material produced by an expanding method.
  • the grid is composed of two projecting end portions having projections and a flat intermediate portion located between the two end portions, and the thickness of the end portion is the thickness of the intermediate portion.
  • the thickness of the intermediate portion is H2 and the difference between the thickness of the end portion and the thickness of the intermediate portion is H1
  • the ratio H1 / H2 to H2 is 3% to 9%. Is preferred.
  • the thickness of the end portion refers to the maximum thickness of the protruding end portion.
  • the electrode plate is designed so that the end part is formed with a protrusion to be a protruding end part having a protrusion, and the thickness of the end part of the electrode plate is set to the thickness of the other part of the electrode plate.
  • the pitch between the positive electrode plate and the negative electrode plate is appropriately increased, so that a battery electrode plate having a good capacity, cycle life and charging efficiency can be provided.
  • the reaction space can be increased, more sulfuric acid can be retained, and the capacity can be increased by allowing the reaction to be performed for a longer period of time.
  • both ends of the electrode plate are thick, the lattice bones at the lattice cutting portions at both ends are far from the electrode plate surface, and it is difficult to cause a short circuit by breaking through the separator, and the strength of both ends is also increased. It is possible to bring about an effect of suppressing the growth of the lattice (the growth of the lattice bone), thereby improving the cycle life. Furthermore, since both ends are thick, a certain gap can be provided between the middle part of the electrode plate and the separator, which is advantageous for sending out oxygen gas during charging, and oxygen gas cannot be diffused immediately. In addition, charging efficiency can be increased by suppressing a reduction in charging efficiency due to loss of oxygen gas.
  • the battery charges normally, some of the electricity is used for lead sulfate reaction and some is used for water decomposition, but oxygen gas cannot be immediately transported to the negative electrode. Gas tends to accumulate, resulting in the following two things. That is, for one thing, the oxygen gas accumulates, thereby inhibiting the reaction of lead sulfate and affecting the chemical conversion efficiency. Second, when oxygen gas accumulates, the oxygen gas cannot be immediately diffused to the negative electrode, and the oxygen gas flows away, resulting in moisture loss. Both of the above two things reduce the charging efficiency.
  • the charging efficiency refers to the ease of lead sulfate reaction and the efficiency of oxygen gas circulation.
  • FIG. 1 is a schematic diagram of Embodiment 1 of a battery electrode plate according to the present invention.
  • the thickness of the intermediate portion of the electrode plate is H2
  • the difference between the thickness of the end portion of the electrode plate and the thickness of the intermediate portion is H1
  • the width of the end portion of the electrode plate is H3.
  • the width of the entire electrode plate is H4.
  • the protrusions of each of the two protrusion-shaped end portions are formed on the same side of the electrode plate, and are formed by being cut by a rotary cut method in a cutting process described later. It is preferable.
  • FIG. 2 is a schematic view of Embodiment 2 of the battery electrode plate according to the present invention.
  • the shape of each of the two protrusion-shaped ends is different from the shape of the protrusion shown in FIG. Are formed on different sides.
  • the protrusion is preferably formed by being cut by a punching method in a cutting step described later.
  • FIG. 3A is a perspective view of the battery electrode plate according to the first embodiment of the present invention.
  • FIG. 3B is a front view of the battery electrode plate shown in FIG.
  • FIG. 3C is a cross-sectional view of the battery electrode plate shown in FIG.
  • the electrode plate comprises two protruding end portions having protrusions and a flat intermediate portion located between the two end portions, The end portion is thicker than the intermediate portion.
  • the protrusions of the two protrusion-shaped end portions can be formed by a current collector and / or an active material layer held by the current collector. From the viewpoint of simplification of the process and cost reduction, Is preferably composed only of an active material layer.
  • the thickness of the protrusion is the difference H1 in the thickness, and if the H1 is within a certain range, an appropriate gap is provided between the separator and the electrode plate, thereby effectively improving the charging efficiency. Can increase, prevent short circuit and increase capacity. If H1 is too large, the active material at both ends protrudes excessively, which increases the risk of short-circuiting, and excessively increases the gap between the electrode plates, leading to a loss of water in the battery and adverse effects. End up. On the other hand, if H1 is too small, the difference in thickness between the two end portions and the intermediate portion is not clear, and the charging efficiency cannot be increased effectively, and the effect of suppressing the growth of the grid of the electrode plate is also obtained. It will not be possible.
  • the ratio H1 / H2 of H1 to H2 is preferably 3% or more and 9% or less. Furthermore, when the ratio H1 / H2 is 3% to 9%, the battery capacity can be increased by about 10% to 20% compared to the case where the ratio H1 / H2 is 0, but the effect is better. In view of the above, the ratio H1 / H2 is more preferably 4% or more and 8% or less.
  • the shape of the protrusion is not particularly limited as long as it can form a protruding end, and may be, for example, a dome shape or a mountain shape.
  • the thickness of the protrusion refers to the maximum thickness at the apex of the protrusion.
  • the width of the protrusion is the width H3 of the end of the electrode plate. If the H3 is too large, the production is difficult and the gap between the separator and the electrode plate is too large. The expansion of the active material in the electrode plate group cannot be effectively suppressed, and the active material cannot be effectively prevented from falling off, which may lead to deterioration of the cycle life of the battery. On the other hand, if the H3 is too small, the stress at both ends of the electrode plate becomes too small, and the growth of the grid of the electrode plate cannot be effectively suppressed, so that the battery capacity becomes unstable. The cycle life is also deteriorated. Therefore, in view of the above two points, the ratio H3 / H4 is preferably 5% or more and 25% or less, and more preferably 10% or more and 20% or less.
  • the electrode plate may be a positive electrode plate or a negative electrode plate, but is preferably a positive electrode plate. This is due to the following reason. That is, in a lead storage battery, gas is generated at the positive electrode, the grid of the positive electrode plate is easy to grow (lattice bone is easy to stretch), short circuit is easily generated, and the battery capacity depends on the positive electrode. This is because, when the protrusion is formed on the plate, the effect can be exhibited more than the negative plate.
  • the protrusions of each of the two protruding end portions may be formed on the same side of the electrode plate or may be formed on different sides of the electrode plate, but the former is preferable. This is due to the following reason. That is, the gap formed in the state where the two protrusions are formed on the same side of the electrode plate is larger than the gap formed in the state where the two protrusions are formed on different sides of the electrode plate, and more sulfuric acid is added.
  • the electrode plate in such a state can increase the charging efficiency of the battery, and also has a significant suppression effect on the end of the battery life in a very short time. Therefore, a better effect can be obtained with respect to the obtained electrode plate group and the performance of the battery using the electrode plate group.
  • the protrusions may be formed by designing process conditions in the method for manufacturing the electrode plate, or by designing the configuration of the active material layer.
  • the main steps are as shown in FIGS. 4A and 4B, and the following steps are performed: (1) From lead or lead alloy using a reciprocating punching die.
  • the lead tape 27 is repeatedly punched to form a plurality of slits along the length direction of the lead tape, and at the same time, the slits are spread in a direction perpendicular to the surface of the lead tape so that the plurality of line portions intersect.
  • Spanned grid was cut into plates having the ears 9, comprising namely a cutting step of obtaining an electrode plate 2a of the unformed, the.
  • the unformed electrode plate 2a is cured, dried and formed to obtain an electrode plate.
  • Chemical conversion may be performed after preparing the electrode plate group using the unformed positive electrode plate and the negative electrode plate and disposed in the battery case of the lead storage battery, or may be performed before preparation of the electrode plate group, The former is preferred.
  • thicknesses refer to thicknesses of the respective parts after the battery becomes a finished product and when the finished battery product is not used.
  • the projections of the two projecting end portions according to the present invention are formed simultaneously with the cutting step, that is, can be formed by designing the process conditions of the cutting step.
  • the protrusion can be formed by cutting with a rotary cut method in the cutting step, or can be formed by cutting with a punching method in the cutting step.
  • FIG. 5 is a schematic diagram showing a case where cutting is performed by a rotary cut method in the cutting step.
  • the rotary cutting device used in the rotary cutting method includes a rotary cutting tool 5 and a support roller 4, and the rotary cutting tool 5 has a blade 5 a formed on the roller 3 and the roller 3 at regular intervals. It consists of.
  • both the rotary cutting tool 5 and the support roller 4 rotate around their respective circle centers as shown by the arrows in FIG.
  • the electrode plate base material filled with the lead paste 24a is subjected to the cutting force of the blade 5a of the rotary cutting tool 5 and the supporting force of the support roller 4, thereby cutting the lead plate 2 into the electrode plate 2a.
  • the lead plate 2 is transported along the direction of the apparatus at a constant speed, and the rotary cutting tool 5 rotates at a speed suitable for it above the lead plate 2, so that the rotating blade 5a becomes the lead plate. 2 is cut at a certain distance, thereby obtaining the electrode plate 2a, and at the same time, protrusions 6 formed by the blade pushing away the active material at the time of cutting are formed at both ends of the electrode plate 2a.
  • FIG. 5 shows a case where cutting is performed using a single rotary cutting device in the rotary cutting method, but in practice, a plurality of rotary cutting devices may be used at the same time. It is appropriately selected depending on the balance between the conveying speed and the rotational speed of the rotary cutting tool 5 and the required dimensions of the electrode plate.
  • FIG. 6 is a schematic diagram showing a case where cutting is performed using a plurality of the rotary cut devices shown in FIG. 5 in the rotary cut method at the same time. Since the thickness of the projection 6 is related to the angle of the blade 5a, the thickness H1 of the projection finally formed at both ends of the electrode plate in the present invention is also related to the angle ⁇ of the blade 5a.
  • the blade angle ⁇ is preferably 45 ° or greater and 75 ° or less, and more preferably 50 ° or greater and 70 ° or less.
  • the features of the rotary cut method are as follows. That is, the controllability of the forward speed of the lead plate is good, the rotational speed of the rotary cutting tool is synchronized with the lead plate speed, it is easy to adjust, and an electrode plate having a large width dimension (for example, 64 mm to 140 mm) is easy to produce.
  • the thickness of the electrode plate and the protrusion can be controlled by controlling the processing speed and the gap between the rotary cut tool and the support roller.
  • FIG. 7 is a perspective view schematically showing a case where cutting is performed by a punching method in the cutting step.
  • FIG. 8 is a front view corresponding to FIG.
  • the punching die used when cutting the electrode plate by the punching method is composed of an upper die and a lower die, the upper die is a movable die 7 and the lower die is a fixed die 8.
  • the movable mold 7 moves up and down, and the lead plate 2 passing between the movable mold 7 and the fixed mold 8 is subjected to the shearing force of the movable mold 7 and the supporting force of the fixed mold 8 to lead.
  • the plate 2 is cut into the electrode plate 2a.
  • the movable mold 7 is formed by performing punching and cutting downward at regular intervals above the lead plate 2 to obtain the electrode plate 2a and at the same time punching the movable mold 7 during cutting. Protrusions 6 are formed at both ends of the electrode plate.
  • the punching method requires that the lead plate advance speed and the upper die punching cutting speed be synchronized. Therefore, the production controllability is slightly inferior and the width dimension is small (for example, 29 mm to 44.5mm) Suitable for production of electrode plates, but production speed is fast.
  • the punching method normally, in the punching method, the protrusions are formed on different sides of both ends of the electrode plate. As described above, the effect that can be realized in such a state is inferior to the effect that can be realized in a state where the protrusion is formed on the same side of both end portions of the electrode plate.
  • the punching method has the following disadvantages as compared with the rotary cutting method. That is, the punching stress is large, and particularly the cutting force (punching force) at both ends of the electrode plate is large, so that the active material at both ends of the electrode plate and the lattice loosen after cutting and the active material falls off. As a result, the cycle life may be reduced.
  • the density of the active material layer i.e. lead paste density is preferably no greater than 4.15 g / cm 3 or more 5.0g / cm 3, 4.25g / cm 3 or more 4.8 g / cm 3 The following is more preferable.
  • the lead paste density in such a range is higher than the normal lead paste density.
  • the lead paste compositions of the two are different, and the density of the lead paste used for forming the protrusions is also different. That is, since the lead paste compositions of the positive electrode plate and the negative electrode plate are different, even if the lead paste densities of the two are the same and the cutting method is the same, the degree of protrusion obtained after cutting is different. Moreover, since the lead paste of the negative electrode plate needs to have a large change in the ratio of the composition components depending on the characteristics actually required, even if the lead paste density is the same, it can be obtained if the ratio of the composition components is different. The degree of protrusion is different.
  • the electrode plate is a positive electrode plate
  • a lead paste density of the positive electrode plate is preferably from 4.15 g / cm 3 or more 4.45g / cm 3, 4.25g / cm 3 or more More preferably, it is 4.35 g / cm 3 or less.
  • the present invention provides a method for producing the electrode plate according to the present invention, wherein the method cuts the electrode plate by a rotary cut method in the cutting step of the electrode plate, and uses the blade of the rotary cut tool used in the rotary cut method.
  • the angle is preferably 45 ° or greater and 75 ° or less, and more preferably 50 ° or greater and 70 ° or less.
  • the density of the active material in order to ensure the strength of the active material at both ends and to keep the protrusions formed at both ends of the electrode plate when cutting the electrode plate, the density of the active material is increased, it is preferred that the density or lead paste density below 4.15 g / cm 3 or more 5.0 g / cm 3, and more preferably to 4.25 g / cm 3 or more 4.8 g / cm 3 or less. Therefore, it is preferable that the electrode plate is a positive electrode plate, a lead paste density of the positive electrode plate is preferably from 4.15 g / cm 3 or more 4.45g / cm 3, 4.25g / cm 3 or more More preferably, it is 4.35 g / cm 3 or less.
  • the present invention further provides an electrode plate group, wherein the electrode plate group is formed by alternately arranging a plurality of positive electrode plates and a plurality of negative electrode plates via separators, and at least the positive electrode plate is the electrode plate of the present invention. It is. In particular, from the viewpoint of improving charge / discharge efficiency and cost reduction, it is preferable that the outermost sides of the electrode plate group are both negative electrode plates. That is, in this case, the number of the negative electrode plates is one more than that of the positive electrode plates. Furthermore, in this way, the active material of the positive electrode plate has a relatively large space, the chemical reaction of the positive electrode plate is more intense than the chemical reaction of the negative electrode plate, and the volume change of the active material before and after the reaction is large. The plate is sandwiched between the negative electrode plates, and the discharges on both sides thereof become uniform, thereby reducing the warpage of the positive electrode plate and the falling off of the active material.
  • the present invention further provides a lead storage battery, wherein the lead storage battery includes the electrode plate group.
  • the lead storage battery of the present invention may be a vent type lead storage battery or a control valve type lead storage battery, but is preferably a control valve type lead storage battery.
  • the lead-acid battery of the present invention is characterized by including the electrode plate group, and other known structures and manufacturing methods can be used, and there is no particular limitation.
  • the lead storage battery can be assembled by the following method. That is, a plurality of positive electrode plates and a plurality of negative electrode plates are alternately overlapped with each other via a separator structure to obtain an electrode plate group. Then, the positive electrode ears having the same polarity in each electrode plate group are welded with a metal plate such as lead, aluminum or copper material by fusion welding or cast welding to obtain a positive electrode strap, and the same polarity in each electrode plate group The negative electrode ear portion is welded with a metal plate such as lead, aluminum, or copper by fusion welding or cast welding to obtain a negative electrode strap.
  • Each electrode plate group is accommodated in a plurality of cell chambers partitioned by partition walls in the battery case.
  • each electrode plate group is connected in series, that is, a plurality of cells are connected in series.
  • the positive electrode strap and the negative electrode strap at the last both ends become a positive electrode end and a negative electrode end, respectively.
  • the positive terminal is connected to a positive terminal, and the negative terminal is connected to a negative terminal.
  • the electrolytic solution is sulfuric acid having a concentration of 1.1 to 1.4 g / ml, and may contain an additive such as silicon dioxide.
  • Example 1- Production of positive electrode plate Positive electrode lead paste as a positive electrode active material by kneading raw material lead powder (a mixture of lead and lead oxide), water and dilute sulfuric acid in a weight ratio of about 100: 12: 14 Got.
  • a lead tape containing a Pb alloy containing about 0.07 mass% Ca and about 1.3 mass% Sn obtained by casting was extruded to a thickness of 1.3 mm.
  • the lead tape 27 is repeatedly punched with a reciprocating punching die, and a plurality of slits are formed along the length direction of the lead tape.
  • the slit was widened in a direction perpendicular to the surface of the lead tape, thereby forming a mesh sheet having a mesh 25 constituted by a plurality of linear portions intersecting each other.
  • the mesh sheet was shaped with a pair of shaping rollers to obtain an expanded lattice.
  • the lead plate 24 was formed by filling the mesh 25 with the lead paste 24a as the positive electrode active material along the length direction of the lattice on the expanded lattice. Then, the lead plate 2 was cut by a rotary cut method to obtain a positive electrode plate having positive electrode ears 9. At this time, the rotary angle of the used rotary cutting tool was 45 °, and protrusions were formed on both end portions on the same side of the positive electrode plate. Curing, drying, and chemical conversion were performed on the positive electrode plate formed by cutting in this way to obtain a positive electrode plate in which the positive electrode active material layer was held on the grid of the positive electrode plate. The chemical conversion may be performed before the electrode plate group is assembled, or may be performed after the electrode plate group is assembled and disposed in the battery case of the lead storage battery.
  • the thickness ratio H1 / H2 of the obtained protrusion was 3%
  • the width ratio H3 / H4 was 15%
  • the density of the obtained lead paste was 4.3 g / cm 3 .
  • a negative electrode lead paste as a negative electrode active material was obtained by kneading raw material lead powder, water and dilute sulfuric acid at a weight ratio of about 100: 10: 4.
  • a negative electrode plate expanded grid as a negative electrode current collector is prepared by a reciprocating type expansion method similar to the positive electrode plate. did.
  • the negative electrode lead paste was filled in the expanded lattice of the negative electrode plate, the expanded lattice (that is, the lead plate) filled with the lead paste was cut by a rotary cut method to obtain a negative electrode plate having a negative electrode ear.
  • the blade angle of the used rotary cut tool was 40 °.
  • an unformed negative electrode plate was obtained. Curing, drying, and chemical conversion were performed on the unformed negative electrode plate to obtain a negative electrode plate in which the negative electrode active material layer was held on the lattice of the negative electrode plate.
  • the chemical conversion may be performed before the electrode plate group is assembled, or may be performed after the electrode plate group is assembled and disposed in the battery case of the lead storage battery.
  • the obtained negative electrode plate has a flat surface and a uniform thickness, and no protrusion is formed at the end of the negative electrode plate. Therefore, the thickness ratio H1 / H2 of the end is 0, and the width ratio. H3 / H4 was 0.
  • the lead paste density of the obtained negative electrode plate was 4.8 g / cm 3 .
  • each electrode plate group obtained as described above positive electrode ears having the same polarity were welded to obtain positive electrode straps, and negative electrode ears having the same polarity were welded to obtain negative electrode straps.
  • Six electrode plate groups were accommodated in six cell chambers partitioned by partition walls in the battery case. Two negative electrode groups adjacent to each other were connected in series by welding the negative electrode strap of one electrode plate group to the positive electrode strap of the adjacent electrode plate group. In this manner, each electrode plate group was connected in series. That is, each cell was connected in series.
  • the positive electrode strap of one electrode plate group is connected to the positive electrode terminal and the negative electrode strap of the other electrode plate group is connected to the negative electrode. Connected to the terminal. Thereafter, a battery lid was attached to the opening of the battery case. Then, sulfuric acid having a concentration of 1.242 g / ml was injected into each cell from a liquid mouth provided on the battery lid as an electrolytic solution, and chemical conversion was performed in the battery case. After the formation, a lead storage battery was obtained by fixing a valve for releasing the gas and pressure generated inside the battery to the liquid mouth part. The battery has a capacity of 65 Ah and a rated voltage of 12V.
  • the cycle life measurement method is as follows.
  • the degree of the electrolyte reaction effect is specifically indicated by the discharge capacity of the battery, and the good or bad of the electrolyte reaction effect can be expressed by measuring the discharge capacity of the battery.
  • the battery capacity is measured as follows.
  • the measurement method of charging efficiency (charging time) is as follows.
  • the battery was charged at a constant voltage of 13.7 V at 25 ° C., and when the charging current became 0.003 times or less of the rated capacity, it was determined that the battery was fully charged, and charging was terminated.
  • the time from the start of charging to the end of charging was defined as the charging time (the unit is time, simply written as h). In general, the charging efficiency is better when the charging time is shorter.
  • Examples 2 to 4 The blade angle of the rotary cutting tool used in the step of cutting the positive electrode plate was increased to 50 ° to 60 °, and the thickness ratio H1 / H2 of the protrusions obtained was increased to 4% to 6%.
  • an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 5 In the cutting process of the positive electrode plate and the negative electrode plate, a punching method was used for both. Except that, an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 4.
  • Examples 6 to 8- The blade angle of the rotary cutting tool used in the cutting process of the positive electrode plate was increased to 65 ° to 75 °, and the thickness ratio H1 / H2 of the protrusions obtained was increased to 7% to 9%.
  • an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 1 Reduce the blade angle of the rotary cutting tool used in the cutting process of the positive electrode plate and the negative electrode plate to 40 °, or use the punching method in the cutting process of the positive electrode plate and the negative electrode plate, and do not form the protrusions. That is, the ratio H1 / H2 and the ratio H3 / H4 in the positive electrode plate and the negative electrode plate were all 0, and the lead paste density of the positive electrode plate was 4.2 g / cm 3 . Other than that, an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 2 The blade angle of the rotary cutting tool used in the cutting process of the positive electrode plate was reduced to 40 °, and the thickness ratio H1 / H2 of the obtained protrusion was reduced to 1%.
  • an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 5 and Example 4 have the same ratio H1 / H2 and ratio H3 / H4 of the protrusions formed on the positive electrode plate and the negative electrode plate, respectively, and only the cutting method used is different. From the results obtained in Example 4 and Example 5, the protrusions are formed by the punching method in the electrode plate cutting process, and the thickness and width of the obtained protrusions are set within a certain range. As a result, the cycle life, capacity, and charging efficiency of the battery can be improved, but it can be seen that the improvement in the effect is slightly inferior to the case where the protrusion is formed by the rotary cut method under the same conditions.
  • Examples 9 to 14- The blade angle of the rotary cutting tool used in the cutting process of the positive electrode plate is kept at 60 °, the thickness ratio H1 / H2 of the obtained protrusion is kept at 6%, and the lead paste density of the positive electrode plate is 4.15 g / cm 3.
  • the width ratio H3 / H4 of the obtained protrusions was changed within the range of 5% to 25%, while changing within the range of ⁇ 4.45 g / cm 3 .
  • an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 15- The blade angle of the rotary cutting tool used in the cutting process of the positive electrode plate is set to 60 °, the thickness ratio H1 / H2 of the obtained protrusion is set to 6%, and the lead paste density of the positive electrode plate is set to 4.3 g / cm 3.
  • the width ratio H3 / H4 of the protrusions to be made was 15%.
  • the blade angle of the rotary cutting tool used in the cutting process is set to 60 °
  • the thickness ratio H1 / H2 of the obtained protrusion is set to 6%
  • the lead paste density of the negative electrode plate is 5.0 g. / to cm 3
  • a width ratio H3 / H4 of projections obtained was 15%.
  • an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 15 The arrangement of the positive electrode plate of Example 15 is exactly the same as that of Example 4, except for the arrangement of the negative electrode plate. Comparing Example 15 with the results obtained in Example 4, by forming appropriate protrusions on both the positive electrode plate and the negative electrode plate, compared to the case of forming protrusions only on the positive electrode plate or the negative electrode plate, It can be seen that the cycle life, capacity and charging efficiency of the battery can be further improved.
  • Example 16- In the cutting process of the positive electrode plate, a punching method is adopted, the thickness ratio H1 / H2 of the protrusions formed at both ends of the positive electrode plate is 2.5%, and the lead paste density of the positive electrode plate is 4.3 g / cm 3. The width ratio H3 / H4 of the resulting protrusion was 5%. Moreover, although the punching method was used also in the negative electrode plate, no protrusion was formed. Other than that, an electrode plate group and a lead storage battery were produced by the same arrangement and manufacturing method as in Example 1.
  • Example 16 From the results obtained in Example 16, by forming protrusions by a punching method in the cutting process of the electrode plate, and setting the thickness and width of the protrusions to be within a certain range, It can be seen that cycle life, capacity and charging efficiency can be improved.
  • a lead storage battery having a good cycle life, capacity and charging efficiency can be effectively produced at low cost by simple adjustment of the process.
  • the present invention provides a battery electrode plate having a simple process, low cost, good capacity, cycle life, and charging efficiency, and a lead-acid battery having the electrode plate. It can be applied to power sources for electric bicycles, electric motorcycles, electric scooters, moped electric motorcycles, and the like.

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PCT/JP2013/000323 2012-02-29 2013-01-23 電池用極板及びその製造方法、該極板を有する極板群並びに鉛蓄電池 WO2013128793A1 (ja)

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CN109546240A (zh) * 2018-11-29 2019-03-29 陈明 一种铅酸蓄电池组修复仪
WO2022267503A1 (zh) * 2021-06-26 2022-12-29 宁德时代新能源科技股份有限公司 电化学装置、电子装置
US11652199B2 (en) 2018-10-16 2023-05-16 Lg Energy Solution, Ltd. Ultrathin foil transferring and processing method capable of reducing curling of ultrathin foil and preventing folding thereof

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CN114566724B (zh) * 2022-01-27 2023-09-15 淄博火炬能源有限责任公司 铅酸电池正极活性物质修复方法
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