WO2015045313A1 - Lead acid storage battery - Google Patents

Lead acid storage battery Download PDF

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Publication number
WO2015045313A1
WO2015045313A1 PCT/JP2014/004687 JP2014004687W WO2015045313A1 WO 2015045313 A1 WO2015045313 A1 WO 2015045313A1 JP 2014004687 W JP2014004687 W JP 2014004687W WO 2015045313 A1 WO2015045313 A1 WO 2015045313A1
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Prior art keywords
electrode plate
lead
positive electrode
battery
density
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PCT/JP2014/004687
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French (fr)
Japanese (ja)
Inventor
勤超 孫
昊 ▲呉▼
陽隆 阿部
佐々木 健浩
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パナソニックIpマネジメント株式会社
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Publication of WO2015045313A1 publication Critical patent/WO2015045313A1/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/14Electrodes for lead-acid accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/431Inorganic material
    • H01M50/434Ceramics
    • H01M50/437Glass
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/06Lead-acid accumulators
    • H01M10/12Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/70Carriers or collectors characterised by shape or form
    • H01M4/72Grids
    • H01M4/73Grids for lead-acid accumulators, e.g. frame plates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • H01M50/44Fibrous material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a lead storage battery, and specifically to a lead storage battery excellent in both life characteristics, charge efficiency characteristics, and high rate discharge characteristics.
  • Lead-acid batteries are not only used as power sources for starting vehicles, lighting power sources, and standby power sources, but are also widely used as main power sources, that is, as independent power sources for charging and discharging facilities.
  • electric power storage devices such as electric vehicles, electric forklifts, electric buses, electric bicycles, electric motorcycles, electric scooters, small electric mopeds, golf cars, electric locomotives, and solar batteries.
  • the characteristics when the lead-acid battery operates are that the current at start-up is large, the discharge current at travel is small, and the discharge time is long. At the same time, maintenance of lead-acid batteries and a long cycle life are required.
  • the pressure applied to the electrode plate group is increased, and the positive electrode active material is suppressed by a separator, thereby suppressing the expansion of the positive electrode active material and preventing the positive electrode active material from falling off. It has become.
  • the size of the battery increases, it is necessary to change the material or increase the thickness of the battery case wall in order to strengthen the battery case. Nevertheless, it is difficult to apply and maintain an appropriate pressure on the electrode plate group.
  • corrosion occurs due to oxidation of the positive electrode current collector, thereby reducing the cross-sectional area of the positive electrode current collector and reducing the overall conductivity of the positive electrode plate. As a result, voltage characteristics when the battery performs high rate discharge deteriorates. When such corrosion of the positive electrode current collector proceeds, the positive electrode current collector itself is eventually broken. Therefore, the capacity of the battery is quickly reduced and the life is reached.
  • the battery performance gradually decreases.
  • the internal pressure of the battery may increase, and a large pressure is applied between the positive electrode plate and the negative electrode plate.
  • the electrode unit is easily compressed or deformed. That is, the electrode unit tends to be broken when the internal pressure of the battery increases.
  • CN201820837U a Chinese utility model patent, discloses a flexible paste blocking plate for double-sided coating.
  • the problems that it tries to solve are as follows. That is, the operation surface at the lower end of the conventional paste shielding plate is flat, and when the paste is dispensed, the lead paste has a predetermined pressure, so the electrode plate is recessed downward, and the distance between the paste blocking plate and the middle of the electrode plate is The amount of intermediate paste becomes relatively large.
  • the raw electrode plate after double-sided coating is thick in the middle and thin at both ends, and after curing, the electrode plate is severely curved, affecting the quality of the electrode plate.
  • the above-described flexible paste blocking plate such as double-sided coating is provided with a paste blocking plate and a paste blocking plate, and has a paste outlet for electrode paste, and the paste outlet penetrates the paste blocking plate up and down.
  • the working surface at the lower end of the paste-blocking plate has an arc shape protruding outward, and the operating surface having an arc shape protruding outward compensates for the deformation amount of the electrode plate in combination with the electrode plate recessed downward, and the thickness of the electrode plate paste Is basically the same and is characterized by enhancing the quality of the product.
  • CN 201906687U which is a utility model patent in China, discloses an eccentricity adjusting device that controls the thickness of the electrode plate with a coating machine. During actual use, the eccentricity adjusting device can detect the thickness of the electrode plate at random. When wave motion occurs, the thickness of the electrode plates passing through the coating machine is matched by making dynamic adjustments without stopping the equipment.
  • Japanese Unexamined Patent Publication No. 57-21068 discloses a method for producing a positive electrode for a sealed lead-acid battery. That the lead paste density is 3.0 to 3.4 g / cm 3 (usually the lead paste density is 3.7 to 4.1 g / cm 3 ) and the active material, the lead paste is filled in the lattice.
  • the problem to be solved by the method is to increase the porosity of the positive electrode plate by reducing the density of the lead paste of the positive electrode plate and improve the rapid discharge characteristics of the sealed lead-acid battery.
  • an aqueous dispersion of polytetrafluoroethylene (PTFE) was added to the lead paste in order to suppress the shortening of the life due to the decrease in the density of the lead paste.
  • PTFE polytetrafluoroethylene
  • Japanese Patent Publication No. 58-223259 discloses a method for manufacturing a lead-acid battery plate. After filling a band-shaped expanded lattice plate made of lead or a lead alloy with lead paste as an active material, it is pressed and compressed into a cutting part having a certain width at a predetermined interval in the length direction, and the cutting The center of the part is cut to produce a single electrode plate, which is then dried. As shown in FIG. 4 of the document, the electrode plate manufactured by the manufacturing method is thinner at both end portions than the intermediate portion.
  • the problem to be solved by the production method is to overcome the disadvantage that the active material has a weak holding power in the conventional cutting part and the active material is easily dropped.
  • Japanese Unexamined Patent 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 that its thickness gradually increases from the one end side to the other end side, but the active material layer has a thickness from the one end side to the other end side. It is formed to become thinner gradually.
  • the thickness of the electrode plate obtained from the sum of the thickness of the lattice body and the thickness of the active material layer covering the lattice body is basically equal from one end side to the other end side of the lattice body.
  • the lead-acid battery electrode plate can prevent the active material layer near the ears covering the grid body from being too thin to expose a part of the grid body, and prevent deterioration of battery performance. Can do.
  • Japanese Unexamined Patent Application Publication No. 2003-86175 discloses a filled electrode plate for a lead storage battery that has no uneven thickness, has no surface irregularities, and has a smooth surface.
  • lead paste which is an active material
  • the packed electrode plate passes between the rollers of the rolling mill to obtain a uniform thickness by pressing the thickness of the packed electrode plate.
  • the deposits and protrusions on both sides of the filling electrode plate become flat.
  • the filled electrode plate for a lead storage battery can better prevent defects such as a short circuit.
  • the surface of the lead-acid battery plate is generally flat and the thickness is uniform, which is advantageous for the performance of the lead-acid battery, and also advantageous for the assembly and charging of the battery. It is considered.
  • a method has been found to some extent in consideration of the design of the electrode plate. For example, as described above, the porosity of the positive electrode plate is increased by reducing the lead paste density of the positive electrode plate. This improves the rapid discharge characteristics of the sealed lead-acid battery. However, reducing the lead paste density leads to a shortened battery life.
  • 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 easily falls off.
  • the capacity cannot be continuously increased because more sulfuric acid accumulates and the chemical reaction cannot proceed better, The designed initial capacity may not be reached.
  • the distance between the positive electrode plate and the negative electrode plate may be too short, causing a short circuit and affecting the cycle life. If the electrode plate is too flat, the separator and the electrode plate are in close contact with each other, and oxygen generated at the end of charging with the positive electrode plate cannot diffuse into the negative electrode, affecting the oxygen reaction and reducing the charging efficiency. To do.
  • CN10593430A a Chinese patent publication, discloses a lead storage battery electrode plate and a method for manufacturing the same.
  • the electrode plate includes two protruding end portions having protrusions and a flat intermediate portion between the both 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
  • the difference between the thickness of the end portion and the thickness of the intermediate portion is H1
  • the value of H1 / H2 which is the ratio of H1 and H2 is 3% to 9%.
  • the electrode plate is designed so that the protrusion is formed at the end and the protrusion has the protrusion, so that the thickness of the end of the electrode plate is made larger than the thickness of the other part. Yes. Therefore, since the space
  • the present invention seeks to provide a lead storage battery in which the life characteristics, charge efficiency characteristics and high rate discharge characteristics of the lead storage battery are improved and the overall performance is greatly improved.
  • An object of the present invention is to provide a lead storage battery having excellent cycle life, charge efficiency, discharge capacity, and high rate discharge characteristics.
  • the above technology is achieved by forming a projection at the end and designing the electrode plate so that the thickness of the end of the electrode plate is larger than the thickness of the other portions and using a high-density separator.
  • the present invention provides the following solutions.
  • a plurality of cell batteries having an electrode plate group, an electrolytic solution, and a cell battery chamber, wherein the electrode plate group and the electrolyte solution are accommodated in the cell battery chamber, and the electrode plate group includes a plurality of positive electrode plates and A plurality of negative electrode plates are alternately arranged via separators, and the positive electrode plate includes a positive electrode current collector having positive electrode ears and a positive electrode active material layer held by the positive electrode current collector,
  • the negative electrode plate is a lead storage battery comprising a negative electrode current collector having a negative electrode ear and a negative electrode active material layer held by the negative electrode current collector,
  • the separator is an AGM separator, and the density of the separator in a state where the electrode group and the electrolytic solution are accommodated in the cell battery chamber is in a range of 117 to 129 g / dm 3 , and the positive electrode plate and the negative electrode plate
  • the current collector of at least one of the electrode plates is an extended grating produced by an extended band method, and the electrode plate
  • the ratio value H1 / H2 is 4% to 8%.
  • the width of the end portion is 5% to 25% of the entire width of the electrode plate.
  • the width of the end portion is 10% to 20% of the entire width of the electrode plate.
  • the protrusions of both the protruding end portions are formed on the same side of the electrode plate.
  • the protrusions of the both projecting end portions are formed on different sides of the electrode plate.
  • the lead paste density which is the density of the active material layer of the electrode plate, is 4.15 g / cm 3 to 5.0 g / cm. It is 3 , It is characterized by the above-mentioned.
  • the electrode plate is a positive electrode plate.
  • the density of the electrolytic solution after the formation of the lead acid battery is 1.33 to 1.35 g / cm 3.
  • the electrode plate is designed so that the thickness of the end portion of the electrode plate is larger than the thickness of the other portions by forming protrusions at the end portions.
  • interval of a positive electrode plate and a negative electrode plate becomes large suitably, the possibility of a short circuit occurrence is reduced significantly, and cycle life improves.
  • more electrolyte solution is accumulated between the positive electrode plate and the negative electrode plate, the chemical reaction proceeds better, the capacity is improved, and oxygen generated at the end of charging in the positive electrode plate can be diffused to the negative electrode in real time. This is advantageous for the reaction and improves the charging efficiency.
  • the distance between the positive electrode plate and the negative electrode plate is not too large, the internal resistance is low.
  • the obtained lead storage battery has excellent cycle life, charge / discharge efficiency, discharge capacity, and high-rate discharge characteristics (that is, high-rate discharge capacity).
  • FIG. 1 schematically shows an electrode plate group using a high-density AGM separator and electrode plates having both protruding end portions in the lead storage battery of the present invention and having both end portions larger in thickness than the intermediate portion.
  • FIG. FIG. 2 is a schematic diagram of Embodiment 1 of the electrode plate for a lead storage battery of the present invention.
  • FIG. 3 is a schematic diagram of Embodiment 2 of the electrode plate for a lead storage battery of the present invention.
  • 4A is a schematic perspective view of the battery electrode plate according to the first embodiment of the present invention
  • FIG. 4B is a front view of the battery electrode plate shown in FIG. 4A.
  • c) is a cross-sectional view of the battery electrode plate shown in FIG.
  • FIG. 5 (a) is a process diagram for manufacturing the extended grating and the electrode plate by the extended method
  • FIG. 5 (b) is a partially enlarged schematic view of the above process.
  • the present invention provides a lead acid battery having a plurality of cell batteries.
  • the lead storage battery includes a plurality of cell batteries having an electrode plate group, an electrolyte solution, and a cell battery chamber, the electrode plate group and the electrolyte solution are accommodated in the cell battery chamber, and the electrode plate group includes a plurality of positive electrodes.
  • the positive electrode plate includes a positive electrode current collector having positive electrode ears, and a positive electrode active material layer held by the positive electrode current collector. And a negative electrode current collector having the negative electrode ear and a negative electrode active material layer held by the negative electrode current collector.
  • the separator is an AGM separator, and the density of the separator in a state where the electrode group and the electrolytic solution are accommodated in the cell battery chamber is in a range of 117 to 129 g / dm 3 , and the positive electrode plate and the negative electrode plate At least one of the electrode plates has the following structure, that is, the current collector of the electrode plate is an extended grating produced by an extended method, and the electrode plate has both protruding end portions having protrusions.
  • 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 thickness of the end portion and the intermediate portion When the difference from the thickness is H1, the ratio H1 / H2 of H1 and H2 is 3% to 9%.
  • the thickness of the end portion refers to the maximum thickness of the protruding end portion.
  • the electrode plate is designed so that the thickness of the end portion of the electrode plate is larger than the thickness of the other portions by forming protrusions at the end portions.
  • interval of a positive electrode plate and a negative electrode plate becomes large suitably, and the electrode plate for batteries which has the outstanding capacity
  • the reaction space can be increased, more sulfuric acid can be accumulated, and the reaction can be performed longer. As a result, the capacity can be improved.
  • both ends of the electrode plate are thick, and the ribs at the grid cutting portions on both ends are far from the surface of the electrode plate, and it is difficult to break the separator and make a short path.
  • both end portions are large, so that there is an action of suppressing the growth of the electrode plate.
  • cycle life can be improved.
  • both ends are thick, a predetermined gap is created between the middle part of the electrode plate and the separator, which is advantageous for oxygen transport during charging, and suppresses reduction in charging efficiency due to simultaneous non-diffusion of oxygen and loss of oxygen. can do.
  • charging efficiency can be improved.
  • a part of the electric power is used for the reaction of lead sulfate and the other part is used for the decomposition of water. If oxygen cannot be transported to the negative electrode in real time, deposition tends to occur.
  • the lead sulfate reaction is inhibited by oxygen deposition. No.2.
  • the charging efficiency here refers to the difficulty of the lead sulfate reaction and the efficiency of oxygen circulation.
  • the lead storage battery is required to have a small interval between the positive electrode plate and the negative electrode plate adjacent to each other in order to give the lead storage battery excellent high rate discharge characteristics.
  • the separator disposed between the positive electrode plate and the negative electrode plate generates a compressive action, which also affects the distribution of the electrolytic solution in the separator. Specifically, if the distance between the positive electrode plate and the negative electrode plate is too small, the separator layer is excessively compressed and only a small amount of the electrolyte can be maintained, so that the discharge capacity is reduced.
  • the separator disposed between the positive electrode plate and the negative electrode plate is recessed, the contact reaction area is reduced, the discharge capacity is reduced, and the high rate discharge characteristics are reduced.
  • At least one of the positive electrode plate and the negative electrode plate in the lead storage battery of the present invention has both projecting end portions, and the thickness of the both end portions is an intermediate portion. Since it is larger than the thickness, the interval between the positive electrode plate and the negative electrode plate is increased, and as a result, the cycle life and the like are improved, but the high-rate discharge capacity of the lead storage battery may be reduced.
  • this inventor discovered that the high-rate discharge characteristic which was excellent in the lead storage battery can be given by arrange
  • an AGM separator is used, and the density of the separator is set in a range of 117 to 129 g / dm 3 . It is clear that the density range is higher than the density of conventional lead-acid battery separators. Furthermore, in the present invention, the upper limit of the density of the separator is set to 129 g / dm 3 because if the separator density is further increased, the cycle of the electrolyte in the separator may be affected. It also affects the lifespan.
  • the density of the separator in the present invention is that which is compressed to a high density of 117 to 129 g / dm 3 when the separator and the electrode plate are pressed to form the electrode plate group. It is determined according to the pressure received in the plate group.
  • the density of the separator basically does not change before and after the formation of the battery.
  • the density of the separator refers to the density after chemical conversion.
  • the material of the glass fiber separator used by the AGM separator is not particularly limited, but a known or commercially available AGM separator for a lead storage battery may be used as long as it meets the requirements of the present invention.
  • the present invention may use a low density electrolytic solution, and the density of the electrolytic solution at the time of liquid injection is 1.24 to 1.26 g / cm 3.
  • the density of the electrolytic solution after the formation of the lead storage battery is preferably 1.33 to 1.35 g / cm 3 .
  • the lead-acid battery can be restored to the density of the electrolyte after the formation of the lead-acid battery after the lead-acid battery is fully charged after a certain period of use.
  • the density of the electrolytic solution refers to the density of the electrolytic solution after the formation of the lead storage battery.
  • the electrolytic solution is preferably an aqueous sulfuric acid solution containing sulfuric acid and water.
  • a small amount of an additive that can be completely dissolved in the electrolytic solution such as silicon dioxide, sodium tetraborate, and sodium sulfate, may be added to the electrolytic solution.
  • the content of the additive in the electrolytic solution is, for example, 0.2 to 1.0 wt%.
  • the lead storage battery of the present invention is preferably a valve-controlled lead storage battery.
  • FIG. 1 schematically shows an electrode plate group using a high-density AGM separator and electrode plates having both protruding end portions in the lead storage battery of the present invention and having both end portions larger in thickness than the intermediate portion.
  • FIG. 1 shows a negative electrode plate having protrusions at both ends, it is preferable that protrusions are actually formed at both ends of the positive electrode plate in the present invention, as will be described later.
  • the electrode group shown in FIG. 1 since the positive electrode plate is covered with the separator and is difficult to see, it is schematically shown by the negative electrode plate exposed to the outside.
  • the state in which the protrusions are formed on both ends of the negative electrode plate is the same as the state in which the protrusions are formed on both ends of the positive electrode plate.
  • FIG. 2 is a schematic diagram of Embodiment 1 of the electrode plate for a lead storage battery of 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 total width of the electrode plate is H4.
  • the protrusions of the both protruding end portions are formed on the same side of the electrode plate and are cut by a hobbing method in a cutting process described later.
  • FIG. 3 is a schematic diagram of Embodiment 2 of the electrode plate for a lead storage battery of the present invention.
  • the shape of the protrusions of each of the two protruding ends is different from that shown in FIG. 1, and the protrusion of each of the protruding ends is different from that of the electrode plate. It is preferable to form by cutting by the press method formed in the side and used for the cutting process mentioned later.
  • FIG. 4A is a schematic perspective view of the battery electrode plate according to the first embodiment of the present invention
  • FIG. 4B is a front view of the battery electrode plate shown in FIG. 4A
  • c) is a cross-sectional view of the battery electrode plate shown in FIG.
  • the electrode plate is composed of both protruding end portions having protrusions and flat intermediate portions between the both end portions.
  • the thickness is greater than the thickness of the intermediate portion.
  • the protrusions of both protruding ends may be formed by a current collector and / or an active material layer held by the current collector, but considering the simplification of the process and the reduction of cost, The protrusion is preferably formed only by the active material layer.
  • the thickness of the protrusion is the thickness difference H1, and if the H1 does not fall within a predetermined range, an appropriate gap cannot be formed between the separator and the electrode plate. Therefore, charging efficiency can be increased, short circuit can be prevented, and cycle life and capacity can be increased.
  • H1 is too large, the active materials at both ends protrude excessively, and on the contrary, the risk of a short circuit increases.
  • the gap between the electrode plates is too large, accelerating the loss of water in the battery, resulting in an adverse effect.
  • H1 is too small, the difference in thickness between the both end portions and the intermediate portion is not clear, and the charging efficiency cannot be improved efficiently. Further, the effect of suppressing the growth of the electrode plate is not clear.
  • the ratio value H1 / H2 of H1 and H2 is 3% to 9%. Further, when the ratio value H1 / H2 is 3% to 9%, the capacity of the battery is about 10% to 20% higher than when the ratio value H1 / H2 is 0. From the viewpoint of better effects, the ratio value H1 / H2 is more preferably 4% to 8%.
  • the shape of the protrusion is not particularly limited, but may be a dome shape, a mountain peak shape, or the like as long as it can form a protruding end.
  • 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, production becomes difficult, and the gap between the separator and the electrode plate is too large. Therefore, the expansion of the active material in the electrode plate group cannot be effectively prevented, and the active material cannot be prevented from falling off. Therefore, the cycle life of the battery is deteriorated. On the other hand, if the H3 is too small, the stress at both ends of the electrode plate is too low to suppress the growth of the electrode plate effectively, resulting in unstable battery capacity and poor cycle life. Therefore, considering the above two points, the ratio value H3 / H4 is preferably 5% to 25%, and more preferably 10% to 20%.
  • the electrode plate may be a positive electrode plate or a negative electrode plate, but is preferably a positive electrode plate. This is because in a lead-acid battery, the positive electrode generates gas, the grid of the positive electrode plate is likely to grow, and short paths are likely to occur. Further, since the capacity of the battery is controlled by the positive electrode, the effect can be further improved when the protrusion is formed on the positive electrode plate as compared with the negative electrode plate.
  • the projections of each of the two projecting ends may be formed on the same side of the electrode plate or may be formed on different sides, but the former is preferable. This is because the gap formed when both protrusions are formed on the same side of the electrode plate is larger than the gap generated when both protrusions are formed on different sides of the electrode plate, and more sulfuric acid is accumulated. Battery capacity can be increased. In addition, the electrode plate in this state can increase the charging efficiency of the battery, and has a remarkable suppression effect on the early expiration of the battery life. Therefore, the performance and effect of the obtained electrode plate group and the battery using the electrode plate group are further improved.
  • the protrusion can be formed by designing the process conditions of the method for manufacturing the electrode plate, and can also be formed by designing the configuration of the active material layer.
  • FIG. 5 (a) and FIG. 5 (b) show main steps in the electrode plate manufacturing method.
  • An unformed electrode plate 2a is obtained by including a filling step and (4) a cutting step of cutting the expanded lattice filled with the lead paste 24a into a positive electrode plate having the polar ears 9.
  • the unformed electrode plate 2a is cured, dried and formed to obtain the electrode plate.
  • Chemical conversion may be performed after the electrode plate group is prepared with the unformed positive electrode plate and the negative electrode plate and attached to the battery case of the lead storage battery, or may be performed before the electrode plate group is manufactured, but the former is preferable. .
  • thickness refers to the thickness of each part when the battery product is not used after being manufactured.
  • the projections of each of the two projecting ends according to the present invention are formed simultaneously with the cutting step, that is, may be formed by designing the process conditions of the cutting step.
  • the protrusion may be formed by cutting with a hobbing method in the cutting step, or may be formed by cutting with a press method in the cutting step.
  • the specific process and advantages and disadvantages of forming the protrusions by the hobbing method or the pressing method are exactly the same as those described in CN10593430A, which is a Chinese patent application, so refer to the related contents of the document. .
  • the hobbing method of the hobbing method and the press method is more preferable.
  • lead paste density is the density of the active material layer is 4.15g / cm 3 ⁇ 5.0g / cm 3, 4.25g / cm 3 ⁇ 4.8g / cm 3 It is more preferable that The lead paste density in the above range is higher than that of normal lead paste.
  • the composition of the lead paste for each of the positive electrode plate and the negative electrode plate is different, and the density of the lead paste for forming the protrusions is also different. That is, since the composition of the lead paste of the positive electrode plate and that of the negative electrode plate are different, even if both lead pastes have the same density, the protrusions are somewhat different after being cut by the same cutting method. Moreover, the lead paste of a negative electrode plate needs to change the ratio of the composition component largely according to the characteristic actually requested
  • the electrode plate is a positive electrode plate, preferably of lead paste density of the positive electrode plate is 4.15g / cm 3 ⁇ 4.45g / cm 3, 4.25g / cm 3 ⁇ 4. More preferably, it is 35 g / cm 3 .
  • the shape, size and height of the protrusion can be controlled by adjusting the cutting process and blade angle of the cutting cutter under the same lead paste density.
  • the structure and composition of other members adopt those of the prior art and are not particularly limited.
  • the lead storage battery can be assembled by the following method.
  • a plurality of the positive plates and the negative plates are alternately overlapped with each other through the separator structure to obtain an electrode plate group.
  • a positive electrode bus is obtained by welding or casting welding the positive electrode ears of the same polarity in a single electrode plate group using a metal plate such as lead, aluminum or copper.
  • a negative electrode bus is obtained by welding or casting welding the negative electrode ears of the same polarity in a single electrode plate group using a metal plate such as lead, aluminum or copper.
  • Each electrode plate group is accommodated in a plurality of cell battery chambers partitioned by partition walls in the battery case.
  • each electrode plate group is connected in series. That is, by connecting a plurality of cell batteries in series, the positive electrode bus and the negative electrode bus at both ends finally 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.
  • electrolyte solution is inject
  • the density of the electrolytic solution at the time of liquid injection is preferably 1.24 to 1.26 g / cm 3
  • the density of the electrolytic solution after the formation of the lead storage battery is 1.33 to 1.35 g / cm 3. Is preferred.
  • the electrolyte solution may contain an additive such as silicon dioxide.
  • Example C (1) Manufacture of positive electrode plate By mixing lead powder (mixture of lead and lead oxide), water, and dilute sulfuric acid as raw materials at a specific gravity ratio of about 100: 12: 14, A positive lead paste is obtained.
  • the Pb alloy lead band containing about 0.07 mass% Ca and about 1.3 mass% Sn obtained by pouring is extruded so as to have a thickness of 1.3 mm.
  • the expanding process is performed, the press is repeatedly performed on the lead band 27 using a reciprocating press mold, and the length of the lead band 27 is increased.
  • a plurality of slits are formed, and the slits are widened in a direction perpendicular to the surface of the lead strip, thereby forming a lattice-like sheet having a mesh 25 in which a plurality of lattice lines intersect.
  • the lattice sheet is shaped using a pair of rollers of a shaping mold to obtain an expanded lattice.
  • the expanded lattice 25 is filled with a lead paste 24a as an active material along the length direction to form the lead plate 2.
  • the lead plate 2 is cut by a hobbing method so that the positive electrode plate having the positive electrode ears 9 is formed, and protrusions are formed at both ends on the same side of the positive electrode plate.
  • the positive electrode plate thus cut is cured, dried, and formed to obtain a positive electrode plate that holds the positive electrode active material with a positive electrode plate lattice.
  • the chemical conversion may be performed before assembling the electrode plate group, or may be performed after the electrode plate group is assembled and attached to the battery case of the lead storage battery.
  • the thickness ratio value H1 / H2 obtained is 3%
  • the width ratio value H3 / H4 is 15%
  • the density of the obtained lead paste is 4.3 g / cm 3 . .
  • a positive electrode lead paste as a positive electrode active material is obtained by mixing lead powder as a raw material, water, and dilute sulfuric acid at a specific gravity ratio of about 100: 10: 4.
  • the parameters of each component of the obtained negative electrode plate refer to values shown in Table 1 described later. Since the surface of the obtained negative electrode plate is flat, the thickness is uniform, and no protrusion is formed at the end of the negative electrode plate, the ratio H1 / H2 of the thickness of the end is 0 and the width The ratio value H3 / H4 is zero.
  • the lead paste density of the obtained negative electrode plate is 4.8 g / cm 3 .
  • the positive electrode ears of the same polarity in the obtained single electrode plate group are welded to obtain a positive electrode bus.
  • a negative electrode ear with the same polarity is welded to obtain a bath.
  • the six electrode plate groups are respectively accommodated in six cell battery chambers partitioned by partition walls in the battery case. By welding the negative electrode bus of the electrode plate group and the adjacent electrode plate group positive electrode bus, two adjacent electrode plate groups are connected in series. Each electrode plate group is connected in series, that is, each cell battery is connected in series.
  • one positive electrode bus of the two electrode plate groups positioned at both ends is connected to the positive electrode terminal, and the other negative electrode bus is connected to the negative electrode terminal.
  • the battery cover is attached to the opening of the battery case.
  • sulfuric acid having a concentration of 1.242 g / cm 3 is injected as an electrolytic solution into each cell battery from a liquid inlet provided in the battery lid, and chemical conversion is performed in the battery case. After the chemical conversion, the density of the electrolytic solution is 1.34 g / cm 3 .
  • a lead storage battery is obtained by fixing the gas generated in the battery and a valve for discharging the pressure to the liquid inlet.
  • the battery has a capacity of 100 Ah and a rated voltage of 12V.
  • the battery After measuring the voltage, internal resistance, and weight of a battery that is new within 30 days after fabrication, the battery is fully charged after 25 A discharge to 10.5 V at an environmental temperature of 25 ⁇ 2 ° C. .
  • the charging is performed at a constant voltage of 14.7 V, and the maximum charging current is 40 A or less.
  • the charging step After completing such a charging step, the charging step is defined as a first cycle.
  • the discharge and charge are repeated again under the above conditions, and the test is terminated when the discharge capacity of the battery reaches 50% of the discharge capacity of the first cycle.
  • the number of charge / discharge cycles performed is calculated, and the number of cycles is defined as the cycle life.
  • the electrolyte reaction effect is reflected in the discharge capacity of the battery, and the measurement of the discharge capacity of the battery indicates whether the electrolyte reaction effect is good or bad.
  • the method for measuring the capacity of the battery is as follows.
  • the environmental temperature is 25 ⁇ 2 ° C., and after discharging 25 A to 10.5 V, the discharge time (unit is hours) And written in h), and the battery capacity is calculated.
  • the method for measuring the charging efficiency is as follows.
  • the charging time (the unit is time, denoted by h). In general, the shorter the charging time, the better the charging efficiency.
  • the high rate discharge characteristic is the high rate discharge capacity.
  • the method for measuring the high rate discharge capacity is as follows.
  • the environmental temperature is 25 ⁇ 2 ° C., and after the discharge of 300 A (3 CA) to 9.6 V, the discharge time ( The unit is time (denoted by h)), and the high rate discharge capacity of the battery is calculated.
  • Example D to I In Examples D to I, except for the ratio H1 / H2 of the ratio of the thickness of the protrusions to a value in the range of 4% to 9%, the electrode plate group and lead under the same installation conditions as Example C A storage battery was produced.
  • Comparative Example A In Comparative Example A, the lead paste density of the positive electrode plate was 4.2 g / cm 3, and neither of the protrusions was formed on the positive electrode plate and the negative electrode plate. That is, the ratio values H1 / H2 and H3 / H4 are both zero. Other than that, an electrode plate group and a lead storage battery were produced by the same installation and process method as in Example C.
  • the lead paste density of the positive electrode plate was set lower than 4.3 g / cm 3 of Example C because no protrusion was formed. However, even if the lead paste density of the positive electrode plate is 4.3 g / cm 3 due to a change in the cutting process, it is possible to realize that no protrusion is formed. However, in this case, productivity is lowered.
  • Comparative Examples B and J an electrode plate group and a lead storage battery were produced under the same installation conditions as in Example C except that the thickness ratio values H1 / H2 of the protrusions were 1% and 10%, respectively. .
  • the obtained lead storage battery As shown in Table 1, from the results obtained in Examples C to I, when the value H1 / H2 of the thickness ratio of the protrusions is in the range of 3% to 9%, the obtained lead storage battery is It can be seen that it has excellent cycle life, charge / discharge efficiency, discharge capacity and high rate discharge capacity at the same time.
  • the ratio H1 / H2 of the thickness ratio of the protrusions is higher than 10%, the distance between the positive electrode plate and the negative electrode plate is too large, that is, the distance between the positive electrode plate and the negative electrode plate is too large, As a result of the active material protruding too much, at least one of the following problems may occur. A short circuit occurs, the amount of moisture lost in the battery increases, and the resistance inside the electrolyte increases.
  • Example L to O an electrode plate group and a lead storage battery were produced under the same installation conditions as Example F, except that the density of the AGM separator was changed from 117 to 129 g / dm 3 .
  • Comparative Examples K, P Comparative Example K, in P, except that the density of the AGM separators respectively 115 g / dm 3 and 131 g / dm 3, others, to prepare a plate group and lead-acid battery at the installation conditions as in Example F.
  • the obtained lead storage battery has excellent cycle life and charge. It can be seen that the discharge efficiency, the discharge capacity, and the high rate discharge capacity are simultaneously provided.
  • Examples R to U In Examples R to U, the density of the electrolytic solution (the value after the formation of the lead storage battery) was changed from 1.33 to 1.35 g / cm 3. A plate group and a lead-acid battery were produced.
  • Comparative Examples Q and V Comparative Examples Q, the V, except that the density of the electrolyte solution (the value after conversion of the lead-acid battery), respectively 1.32 g / cm 3 and 1.36 g / cm 3, and other installation in the same manner as in Example F An electrode plate group and a lead storage battery were produced under the conditions.
  • the density of the electrolytic solution (value after the formation of the lead storage battery) is in the range of 1.33 to 1.35 g / cm 3. It can be seen that the obtained lead storage battery has excellent cycle life, charge / discharge efficiency, discharge capacity and high rate discharge capacity at the same time.
  • the density of the electrolytic solution (value after the formation of the lead storage battery) was lower than 1.33 g / cm 3 or exceeded 1.35 g / cm 3 .
  • the density of the electrolytic solution (the value after the formation of the lead storage battery) is lower than 1.33 g / cm 3 , the reaction is lowered because the sulfate participating in the reaction is insufficient. In addition, the electrolyte is close to neutral during discharging, and dendritic crystal growth is likely to occur during charging.
  • the density of the electrolytic solution (the value after the formation of the lead storage battery) exceeds 1.35 g / cm 3 , the lattice is easily corroded and the ion migration resistance is increased.
  • Comparative Example W In Comparative Example W, the density of the AGM separator was 114 g / dm 3, and the density of the electrolytic solution (value after the formation of the lead storage battery) was 1.31 g / cm 3.
  • the electrode plate group and the lead storage battery were produced under the installation conditions of
  • Comparative Example W the density of the AGM separator and the density of the electrolytic solution are not within the scope of the present invention. This is an example corresponding to the above-described technique in CN10259430A of the Chinese patent application which is the prior art of the present invention.
  • Example X In Example X, protrusions are formed at both ends of the negative electrode plate, the thickness ratio value H1 / H2 of the protrusions is 6%, and the width ratio value H3 / H4 is 15%.
  • the surface of the positive electrode plate is flat, the thickness is uniform, and no protrusion is formed at the end of the positive electrode plate, that is, the value H1 / H2 of the thickness ratio of the end of the positive electrode plate is 0, The width ratio value H3 / H4 is zero.
  • the electrode plate group and the lead storage battery were produced under the same installation conditions as in Example F.
  • Example X As shown in Table 1, as compared with Example F, the cycle life characteristics of the battery in Example X are slightly deteriorated. This is because the negative electrode plate lattice has a lower deformation and growth capability than the positive plate lattice during repeated charge and discharge.
  • Example Y In Example Y, protrusions are formed at both ends of each of the positive electrode plate and the negative electrode plate, the thickness ratio value H1 / H2 of the protrusions is 6%, and the width ratio value H3 / H4 is 15%. is there. Other than that, the electrode plate group and the lead storage battery were produced under the same installation conditions as in Example F.
  • Example Y As shown in Table 1, compared with Example F, the charge / discharge characteristics (discharge efficiency, discharge capacity, and high rate discharge capacity) of the battery in Example Y are slightly lowered. This is because protrusions are formed at both ends of each of the positive electrode plate and the negative electrode plate, the distance between the positive electrode plate and the negative electrode plate is too large, and the resistance increases.
  • the present invention provides a lead storage battery having excellent cycle life, charge / discharge efficiency, discharge capacity, and high-rate discharge capacity, and the lead storage battery is not used as a power source for starting a vehicle, an illumination power source, and a standby power source. It is also widely used as a power source, that is, an independent power source for charging and discharging equipment.
  • electric power storage devices such as electric vehicles, electric forklifts, electric buses, electric bicycles, electric motorcycles, electric scooters, small electric mopeds, golf cars, electric locomotives, and solar batteries.

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Abstract

This lead acid storage battery comprises a plurality of cells, each of which comprises an electrode plate group, an electrolyte solution and a cell chamber. The electrode plate group and the electrolyte solution are contained in the cell chamber. The electrode plate group is obtained by alternately arranging a plurality of positive electrode plates and a plurality of negative electrode plates with separators being interposed therebetween. The separators are AGM separators, and each separator has a density within the range of 117-129 g/dm3. The collectors of the positive electrode plates and/or the negative electrode plates are expanded grids, and each electrode plate is composed of projected end portions each having a projection and a flat intermediate portion between the end portions. The thickness of the end portions is larger than the thickness of the intermediate portion.

Description

鉛蓄電池Lead acid battery
 本発明は、鉛蓄電池に関し、具体的には、寿命特性、充電効率特性及びハイレート放電特性が共に優れた鉛蓄電池に関する。 The present invention relates to a lead storage battery, and specifically to a lead storage battery excellent in both life characteristics, charge efficiency characteristics, and high rate discharge characteristics.
 鉛蓄電池は、車両を起動する電源、照明電源及び予備電源に用いられるだけではなく、主電源用途、即ち、独立した充放電設備用電源としても広く用いられている。例えば、電動自動車、電動フォークリフト、電動バス、電動自転車、電動バイク、電動スクータ、小型電動モペッド、ゴルフ用車、電気機関車等の動力電源、ソーラー用電池等の電気エネルギー蓄積装置である。こういった用途において、鉛蓄電池が動作する際の特徴は、起動時の電流が大きく、走行時の放電電流が小さく、放電時間が長い、ということである。同時に、鉛蓄電池のメンテナンスの低減、長いサイクル寿命が要求される。電池の長寿命化の点において、通常は、極板群にかかる圧力を高くし、セパレータで正極活物質を押さえるなどで、正極活物質の膨張を抑制し、正極活物質の脱落を防止することになっている。しかしながら、電池の大型化に伴い、電槽を強めるために材質を変えたり、電槽壁の厚さを大きくしたりする必要がある。にもかかわらず、極板群に適当な圧力を印加維持することが困難である。鉛蓄電池は、使用時間が長くなるのに伴い、正極集電体の酸化で腐食が発生し、これにより正極集電体の断面積が減少し、正極板全体の導電性が低減する。その結果、電池がハイレート放電を行う際の電圧特性が低下する。このような正極集電体の腐食が進むと、最終的に正極集電体自体に断裂を発生する。よって、電池の容量が速やかに低減し、寿命に至る。 Lead-acid batteries are not only used as power sources for starting vehicles, lighting power sources, and standby power sources, but are also widely used as main power sources, that is, as independent power sources for charging and discharging facilities. For example, electric power storage devices such as electric vehicles, electric forklifts, electric buses, electric bicycles, electric motorcycles, electric scooters, small electric mopeds, golf cars, electric locomotives, and solar batteries. In such an application, the characteristics when the lead-acid battery operates are that the current at start-up is large, the discharge current at travel is small, and the discharge time is long. At the same time, maintenance of lead-acid batteries and a long cycle life are required. In terms of extending the life of the battery, normally, the pressure applied to the electrode plate group is increased, and the positive electrode active material is suppressed by a separator, thereby suppressing the expansion of the positive electrode active material and preventing the positive electrode active material from falling off. It has become. However, as the size of the battery increases, it is necessary to change the material or increase the thickness of the battery case wall in order to strengthen the battery case. Nevertheless, it is difficult to apply and maintain an appropriate pressure on the electrode plate group. As the usage time of lead-acid batteries increases, corrosion occurs due to oxidation of the positive electrode current collector, thereby reducing the cross-sectional area of the positive electrode current collector and reducing the overall conductivity of the positive electrode plate. As a result, voltage characteristics when the battery performs high rate discharge deteriorates. When such corrosion of the positive electrode current collector proceeds, the positive electrode current collector itself is eventually broken. Therefore, the capacity of the battery is quickly reduced and the life is reached.
 鉛蓄電池の使用中、繰り返し充放電を行う場合、電池の性能が次第に低下していく。電池の性能が低下した場合、電池の内圧が上昇することがあり、正極板と負極板との間に大きい圧力が印加してしまう。このとき、電極ユニットが圧縮又は変形しやすくなる。即ち、電極ユニットは、電池の内圧が上昇すると、壊れやすい傾向にある。 If the battery is repeatedly charged and discharged while the lead acid battery is in use, the battery performance gradually decreases. When the performance of the battery deteriorates, the internal pressure of the battery may increase, and a large pressure is applied between the positive electrode plate and the negative electrode plate. At this time, the electrode unit is easily compressed or deformed. That is, the electrode unit tends to be broken when the internal pressure of the battery increases.
 一方、電子機器の小型化及び軽量化の速やかな進展に伴い、電源として用いられる鉛蓄電池には、小体積及び高充放電容量を有することが要求される。電池の正負極板の間の距離を小さくすることは、容量を変化しないまま体積を小さくするための有効な手段であるが、正負極板が近接しすぎると、内部短絡する危険がある。正極板と負極板が短絡すると、電池内部の温度が上昇し、この時、極板群にも安全性を確保する機能が要求される。さらに、電池のパワー特性及び充放電容量を維持する観点から、極板群のイオン透過性、及び電解液を吸収維持する性能を確保する必要がある。 On the other hand, with rapid progress of miniaturization and weight reduction of electronic devices, lead storage batteries used as power sources are required to have a small volume and a high charge / discharge capacity. Reducing the distance between the positive and negative electrode plates of the battery is an effective means for reducing the volume without changing the capacity. However, if the positive and negative electrode plates are too close, there is a risk of internal short circuit. When the positive electrode plate and the negative electrode plate are short-circuited, the temperature inside the battery rises, and at this time, the electrode plate group is also required to have a function of ensuring safety. Furthermore, from the viewpoint of maintaining the power characteristics and charge / discharge capacity of the battery, it is necessary to ensure the ion permeability of the electrode plate group and the performance of absorbing and maintaining the electrolytic solution.
 鉛蓄電池の性能、例えば、サイクル寿命、容量及び充放電効率をいかに高めるかということについては、従来は、格子合金や鉛ペースト配合などの点が既に考慮されている。また、極板の構造や性能が鉛蓄電池の体積、パワー特性、充放電容量及びサイクル寿命に大きく影響するという点から、極板の性能及び構造に対し様々な検討を行ってきた。 Regarding the performance of lead-acid batteries, for example, how to improve cycle life, capacity and charge / discharge efficiency, points such as a lattice alloy and lead paste blending have already been considered. In addition, various studies have been made on the performance and structure of the electrode plate because the structure and performance of the electrode plate greatly affect the volume, power characteristics, charge / discharge capacity, and cycle life of the lead storage battery.
 中国の実用新案特許であるCN201820837Uには、両面塗装用等撓性ペースト遮断板が開示されている。それが解決しようとする課題は以下の通りである。即ち、従来のペースト遮断板の下端の動作面が平面であり、ペーストを出す時、鉛ペーストが所定の圧力を有するので、極板が下方へ凹み、ペースト遮断板と極板中間との距離が大きくなり、中間のペースト量が相対的に多くなる。両面塗装後の生極板は、中間が厚く、両端が薄く、硬化後極板が酷く湾曲し、極板の質に影響する。 CN201820837U, a Chinese utility model patent, discloses a flexible paste blocking plate for double-sided coating. The problems that it tries to solve are as follows. That is, the operation surface at the lower end of the conventional paste shielding plate is flat, and when the paste is dispensed, the lead paste has a predetermined pressure, so the electrode plate is recessed downward, and the distance between the paste blocking plate and the middle of the electrode plate is The amount of intermediate paste becomes relatively large. The raw electrode plate after double-sided coating is thick in the middle and thin at both ends, and after curing, the electrode plate is severely curved, affecting the quality of the electrode plate.
 上記両面塗装等撓性のペースト遮断板は、ペースト遮断板と、ペースト遮断板内に設けられ、極板ペースト用ペースト出口とを備え、上記ペースト出口は上下にペースト遮断板を貫通している。ペースト遮断板の下端の動作面は外へ突起する円弧状であり、外へ突起する円弧状である動作面は下方へ凹む極板と組み合わせて極板の変形量を補い、極板ペーストの厚さが基本的同じで、製品の質を高めることを特徴とする。 The above-described flexible paste blocking plate such as double-sided coating is provided with a paste blocking plate and a paste blocking plate, and has a paste outlet for electrode paste, and the paste outlet penetrates the paste blocking plate up and down. The working surface at the lower end of the paste-blocking plate has an arc shape protruding outward, and the operating surface having an arc shape protruding outward compensates for the deformation amount of the electrode plate in combination with the electrode plate recessed downward, and the thickness of the electrode plate paste Is basically the same and is characterized by enhancing the quality of the product.
 中国の実用新案特許であるCN201906687Uには、塗装機で極板の厚さを制御する偏心調整装置が開示されている。実際の使用中、該偏心調整装置は極板の厚さをランダムに検出することができる。波動が起こると、機器を停止しない状態でダイナミックに調整を行うことで、塗装機を通過する極板の厚さが一致する。 CN 201906687U, which is a utility model patent in China, discloses an eccentricity adjusting device that controls the thickness of the electrode plate with a coating machine. During actual use, the eccentricity adjusting device can detect the thickness of the electrode plate at random. When wave motion occurs, the thickness of the electrode plates passing through the coating machine is matched by making dynamic adjustments without stopping the equipment.
 日本特開昭57-21068号公報には、密閉型鉛蓄電池用正極の製造方法が開示されている。鉛ペーストの密度が3.0~3.4g/cm(通常、鉛ペースト密度が3.7~4.1g/cm)と低い活物質である鉛ペーストが格子に充填されていることを特徴とする。該方法が解決しようとする課題は、正極板の鉛ペーストの密度を低下することで正極板の多孔度を高め、密閉型鉛蓄電池の急速な放電特性を改善することである。しかしながら、鉛ペーストの密度の低下による寿命の短縮を抑制するためには、鉛ペーストにポリテトラフルオロエチレン(polytetrafluoroethylene;PTFE)の水性分散液を添加した。 Japanese Unexamined Patent Publication No. 57-21068 discloses a method for producing a positive electrode for a sealed lead-acid battery. That the lead paste density is 3.0 to 3.4 g / cm 3 (usually the lead paste density is 3.7 to 4.1 g / cm 3 ) and the active material, the lead paste is filled in the lattice. Features. The problem to be solved by the method is to increase the porosity of the positive electrode plate by reducing the density of the lead paste of the positive electrode plate and improve the rapid discharge characteristics of the sealed lead-acid battery. However, an aqueous dispersion of polytetrafluoroethylene (PTFE) was added to the lead paste in order to suppress the shortening of the life due to the decrease in the density of the lead paste.
 日本特公昭58-223259号公報には、鉛蓄電池極板の製造方法が開示されている。鉛又は鉛合金で形成された帯状のエキスパンド格子板に活物質である鉛ペーストを充填した後、長さ方向に所定の間隔をおいて若干の幅を有する裁断部に加圧圧縮し、該裁断部の中心を裁断して単一の極板を作製し、乾燥を行うことを特徴とする。該文献の図4に示すように、該製造方法によって製造された極板は、両端部の厚さが中間部分よりも薄い。該製造方法が解決しよう課題は、従来の裁断部での活物質の保持力が弱く、活物質が脱落しやすいという欠点を克服することである。 Japanese Patent Publication No. 58-223259 discloses a method for manufacturing a lead-acid battery plate. After filling a band-shaped expanded lattice plate made of lead or a lead alloy with lead paste as an active material, it is pressed and compressed into a cutting part having a certain width at a predetermined interval in the length direction, and the cutting The center of the part is cut to produce a single electrode plate, which is then dried. As shown in FIG. 4 of the document, the electrode plate manufactured by the manufacturing method is thinner at both end portions than the intermediate portion. The problem to be solved by the production method is to overcome the disadvantage that the active material has a weak holding power in the conventional cutting part and the active material is easily dropped.
 日本特開2007-258088号公報には、一端側に集電用耳部を有する格子体に活物質を充填した鉛蓄電池用極板が開示されている。上記格子体は、その厚さが上記一端側から他端側に向かって徐々に厚くなるように形成されているが、上記活物質層は、その厚さが上記一端側から他端側に向かって徐々に薄くなるように形成されている。これにより、上記格子体の厚さと該格子体を覆う活物質層との厚さの合計から得られた極板の厚さは、上記格子体の一端側から他端側にまで基本的に等しい。上記鉛蓄電池用極板は、格子体を覆う耳部付近の活物質層の厚さが薄すぎて格子体の一部が露出するのを防止することができ、電池性能の低下を防止することができる。 Japanese Unexamined Patent 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 that its thickness gradually increases from the one end side to the other end side, but the active material layer has a thickness from the one end side to the other end side. It is formed to become thinner gradually. Thereby, the thickness of the electrode plate obtained from the sum of the thickness of the lattice body and the thickness of the active material layer covering the lattice body is basically equal from one end side to the other end side of the lattice body. . The lead-acid battery electrode plate can prevent the active material layer near the ears covering the grid body from being too thin to expose a part of the grid body, and prevent deterioration of battery performance. Can do.
 日本特開2003-86175号公報には、厚さの不均一がなく、表面に凹凸がなくかつ表面が平滑な鉛蓄電池用充填極板が開示されている。基板上に活物質である鉛ペーストを充填し、乾燥工程を行って得られた充填極板が圧延機のローラ間を通ることで、充填極板の厚さを押しつけて均一した厚さを得て、充填極板の両面の付着物及び突起等が平坦になる。上記鉛蓄電池用充填極板は、短絡などの欠点をよりよく防止することができる。 Japanese Unexamined Patent Application Publication No. 2003-86175 discloses a filled electrode plate for a lead storage battery that has no uneven thickness, has no surface irregularities, and has a smooth surface. By filling the substrate with lead paste, which is an active material, and performing the drying process, the packed electrode plate passes between the rollers of the rolling mill to obtain a uniform thickness by pressing the thickness of the packed electrode plate. Thus, the deposits and protrusions on both sides of the filling electrode plate become flat. The filled electrode plate for a lead storage battery can better prevent defects such as a short circuit.
 以上のことから、従来技術では、通常、鉛蓄電池用極板の表面が平坦で、厚さが均一であることが、鉛蓄電池の性能に有利、電池の組立及び充電の化成にも有利だと考えられている。また、従来技術では、極板の設計を考慮して、ある程度方法を見つけた。例えば、上記のように、正極板の鉛ペースト密度を低減することで正極板の多孔度を高める。このことにより、密閉型鉛蓄電池の急速な放電特性を改善する。しかし、鉛ペースト密度の低減は、電池の寿命の短縮につながる。又は、極板の両端部の厚さを中間部分よりも薄くすることで、端部での活物質の保持力が弱く、活物質が脱落しやすいという欠点を克服する。 From the above, in the prior art, the surface of the lead-acid battery plate is generally flat and the thickness is uniform, which is advantageous for the performance of the lead-acid battery, and also advantageous for the assembly and charging of the battery. It is considered. In the prior art, a method has been found to some extent in consideration of the design of the electrode plate. For example, as described above, the porosity of the positive electrode plate is increased by reducing the lead paste density of the positive electrode plate. This improves the rapid discharge characteristics of the sealed lead-acid battery. However, reducing the lead paste density leads to a shortened battery life. 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 easily falls off.
 しかしながら、極板の表面が平坦で、極板の厚さが一致する場合、より多くの硫酸を蓄積して化学反応をより良く進むことができないため、容量が継続的に高めることができず、設計した初期容量に達することもできない可能性がある。また、極板の表面が平坦で、極板の厚さが一致する場合、正極板と負極板との間隔が小さすぎて短絡する虞があり、サイクル寿命に影響を与える。なお、極板が平坦すぎると、セパレータと極板とは過密に接触し、正極板で充電末期に生じた酸素は負極に拡散することができず、酸素の反応に影響し、充電効率が低下する。 However, if the surface of the electrode plate is flat and the electrode plates have the same thickness, the capacity cannot be continuously increased because more sulfuric acid accumulates and the chemical reaction cannot proceed better, The designed initial capacity may not be reached. In addition, when the surface of the electrode plate is flat and the electrode plates have the same thickness, the distance between the positive electrode plate and the negative electrode plate may be too short, causing a short circuit and affecting the cycle life. If the electrode plate is too flat, the separator and the electrode plate are in close contact with each other, and oxygen generated at the end of charging with the positive electrode plate cannot diffuse into the negative electrode, affecting the oxygen reaction and reducing the charging efficiency. To do.
 中国の特許公開であるCN102593430Aには、鉛蓄電池用極板及びその製造方法が開示されている。上記極板は、突起を有する2つの突起状端部と該両端部の間の平坦中間部分とからなり、上記端部の厚さは上記中間部分の厚さよりも大きい。上記中間部分の厚さをH2とし、上記端部の厚さと上記中間部分の厚さとの差をH1とした場合、H1とH2との比であるH1/H2の値は3%~9%である。本発明は、端部に突起が形成され、突起を有する突起状端部となるように極板を設計することで、極板の端部の厚さをその他の部分の厚さよりも大きくしている。よって、正極板と負極板との間隔が適宜に大きくなるため、電池のサイクル寿命、容量及び充電効率を向上した。 CN10593430A, a Chinese patent publication, discloses a lead storage battery electrode plate and a method for manufacturing the same. The electrode plate includes two protruding end portions having protrusions and a flat intermediate portion between the both end portions, and the thickness of the end portion is larger than the thickness of the intermediate portion. When 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 value of H1 / H2, which is the ratio of H1 and H2, is 3% to 9%. is there. According to the present invention, the electrode plate is designed so that the protrusion is formed at the end and the protrusion has the protrusion, so that the thickness of the end of the electrode plate is made larger than the thickness of the other part. Yes. Therefore, since the space | interval of a positive electrode plate and a negative electrode plate becomes large suitably, the cycle life, capacity | capacitance, and charging efficiency of the battery were improved.
 しかしながら、本発明は、鉛蓄電池の寿命特性、充電効率特性及びハイレート放電特性を共に向上し、総合性能が大幅に改善された鉛蓄電池を提供しようとしている。 However, the present invention seeks to provide a lead storage battery in which the life characteristics, charge efficiency characteristics and high rate discharge characteristics of the lead storage battery are improved and the overall performance is greatly improved.
 本発明の目的は、サイクル寿命、充電効率、放電容量及びハイレート放電特性がともに優れた鉛蓄電池を提供することにある。 An object of the present invention is to provide a lead storage battery having excellent cycle life, charge efficiency, discharge capacity, and high rate discharge characteristics.
 本発明は、端部に突起を形成し、極板の端部の厚さがその他の部分の厚さよりも大きくなるように極板を設計するとともに、高密度セパレータを用いることで、上記の技術的課題を解決する。 According to the present invention, the above technology is achieved by forming a projection at the end and designing the electrode plate so that the thickness of the end of the electrode plate is larger than the thickness of the other portions and using a high-density separator. To solve specific problems.
 即ち、本発明は以下の解決手段を提供する。 That is, the present invention provides the following solutions.
 (1)極板群、電解液及びセル電池チャンバーを有する複数のセル電池を有し、前記極板群及び前記電解液は前記セル電池チャンバーに収容され、前記極板群は複数の正極板及び複数の負極板がセパレータを介して交互に配列したものであり、前記正極板は、正極極耳を有する正極集電体と該正極集電体によって保持された正極活物質層とを備え、前記負極板は、負極極耳を有する負極集電体と該負極集電体によって保持された負極活物質層とを備える鉛蓄電池において、
前記セパレータはAGMセパレータであり、前記極板群及び前記電解液が前記セル電池チャンバーに収容され状態での前記セパレータの密度は117~129g/dmという範囲にあり、前記正極板及び前記負極板のうちの少なくとも1つの極板の集電体はエキスバンド法で作製したエキスバンド格子であり、前記極板は突起を有する突起状両端部と該両端部の間の平坦中間部分とを含み、前記両端部の厚さが前記中間部分の厚さよりも大きく、前記中間部分の厚さをH2とし、前記端部の厚さと前記中間部分の厚さとの差をH1とした時に、H1とH2の比の値H1/H2は3%~9%であることを特徴とする。
(1) A plurality of cell batteries having an electrode plate group, an electrolytic solution, and a cell battery chamber, wherein the electrode plate group and the electrolyte solution are accommodated in the cell battery chamber, and the electrode plate group includes a plurality of positive electrode plates and A plurality of negative electrode plates are alternately arranged via separators, and the positive electrode plate includes a positive electrode current collector having positive electrode ears and a positive electrode active material layer held by the positive electrode current collector, The negative electrode plate is a lead storage battery comprising a negative electrode current collector having a negative electrode ear and a negative electrode active material layer held by the negative electrode current collector,
The separator is an AGM separator, and the density of the separator in a state where the electrode group and the electrolytic solution are accommodated in the cell battery chamber is in a range of 117 to 129 g / dm 3 , and the positive electrode plate and the negative electrode plate The current collector of at least one of the electrode plates is an extended grating produced by an extended band method, and the electrode plate includes protruding end portions having protrusions and flat intermediate portions between the both end portions, When the thickness of the both end portions 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, H1 and H2 The ratio value H1 / H2 is 3% to 9%.
 (2)前記(1)に記載の鉛蓄電池において、前記比の値H1/H2は4%~8%であることを特徴とする。 (2) In the lead storage battery according to (1), the ratio value H1 / H2 is 4% to 8%.
 (3)前記(1)に記載の鉛蓄電池において、前記端部の幅は前記極板の全幅の5%~25%であることを特徴とする。 (3) In the lead-acid battery according to (1), the width of the end portion is 5% to 25% of the entire width of the electrode plate.
 (4)前記(3)に記載の鉛蓄電池において、前記端部の幅は前記極板の全幅の10%~20%であることを特徴とする。 (4) In the lead-acid battery according to (3), the width of the end portion is 10% to 20% of the entire width of the electrode plate.
 (5)前記(1)に記載の鉛蓄電池において、前記両突起状端部のそれぞれが有する突起は、前記極板の同一側に形成されていることを特徴とする。 (5) In the lead-acid battery according to (1), the protrusions of both the protruding end portions are formed on the same side of the electrode plate.
 (6)前記(1)に記載の鉛蓄電池において、前記両突起状端部のそれぞれが有する突起は、前記極板の異なる側に形成されていることを特徴とする。 (6) In the lead storage battery according to (1), the protrusions of the both projecting end portions are formed on different sides of the electrode plate.
 (7)前記(1)~(6)の何れか1つに記載の鉛蓄電池において、前記極板の活物質層の密度である鉛ペースト密度は4.15g/cm~5.0g/cmであることを特徴とする。 (7) In the lead acid battery according to any one of (1) to (6), the lead paste density, which is the density of the active material layer of the electrode plate, is 4.15 g / cm 3 to 5.0 g / cm. It is 3 , It is characterized by the above-mentioned.
 (8)前記(1)~(6)の何れか1つに記載の鉛蓄電池において、前記極板は正極板であることを特徴とする。 (8) In the lead storage battery according to any one of (1) to (6), the electrode plate is a positive electrode plate.
 (9)前記(1)に記載の鉛蓄電池において、前記正極板の活物質層の密度である鉛ペースト密度は4.15g/cm~4.45g/cmであることを特徴とする。 (9) In the lead-acid battery according to (1), wherein the lead paste density is the density of the active material layer of the positive electrode plate is 4.15g / cm 3 ~ 4.45g / cm 3.
 (10)前記(1)~(6)の何れか1つに記載の鉛蓄電池において、前記鉛蓄電池の化成後の前記電解液の密度は1.33~1.35g/cmであることを特徴とする。 (10) In the lead acid battery according to any one of (1) to (6), the density of the electrolytic solution after the formation of the lead acid battery is 1.33 to 1.35 g / cm 3. Features.
 (11)前記(1)に記載の鉛蓄電池において、前記電解液は硫酸と水とを含む硫酸水溶液であることを特徴とする。 (11) The lead acid battery according to (1), wherein the electrolytic solution is a sulfuric acid aqueous solution containing sulfuric acid and water.
 (12)前記(1)又は(11)に記載の鉛蓄電池において、前記電解液には、該電解液に完全に溶解可能な少量の添加剤が含まれていることを特徴とする。 (12) The lead-acid battery according to (1) or (11), wherein the electrolyte contains a small amount of an additive that can be completely dissolved in the electrolyte.
 本発明によると、極板は、端部に突起が形成されることで極板の端部の厚さがその他の部分の厚さよりも大きくなるように設計される。これにより、正極板と負極板との間隔が適宜に大きくなり、短絡発生の可能性が大幅に低減され、サイクル寿命が向上する。また、正極板と負極板との間により多くの電解液を蓄積し、化学反応がより良く進み、容量を向上するとともに、正極板で充電末期に生じた酸素がリアルタイムに負極まで拡散でき、酸素の反応に有利であり、充電効率を向上する。同時に、正極板と負極板との間隔は大きすぎないため、内部抵抗が低い。これを基に、高密度のセパレータを用いることで、セパレータにおける空孔の体積(即ち電解液を保持する体積)を確保するとともに、毛細管現象を利用することができる。その結果、得られた鉛蓄電池は、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電特性(即ち、ハイレート放電容量)を有する。 According to the present invention, the electrode plate is designed so that the thickness of the end portion of the electrode plate is larger than the thickness of the other portions by forming protrusions at the end portions. Thereby, the space | interval of a positive electrode plate and a negative electrode plate becomes large suitably, the possibility of a short circuit occurrence is reduced significantly, and cycle life improves. In addition, more electrolyte solution is accumulated between the positive electrode plate and the negative electrode plate, the chemical reaction proceeds better, the capacity is improved, and oxygen generated at the end of charging in the positive electrode plate can be diffused to the negative electrode in real time. This is advantageous for the reaction and improves the charging efficiency. At the same time, since the distance between the positive electrode plate and the negative electrode plate is not too large, the internal resistance is low. Based on this, by using a high-density separator, it is possible to secure the volume of pores in the separator (that is, the volume that holds the electrolyte) and to use the capillary phenomenon. As a result, the obtained lead storage battery has excellent cycle life, charge / discharge efficiency, discharge capacity, and high-rate discharge characteristics (that is, high-rate discharge capacity).
図1は、本発明の鉛蓄電池における高密度AGMセパレータと両突起状端部を有しかつ該両端部の厚さが中間部分の厚さよりも大きい極板を用いた極板群を模式的に示す図である。FIG. 1 schematically shows an electrode plate group using a high-density AGM separator and electrode plates having both protruding end portions in the lead storage battery of the present invention and having both end portions larger in thickness than the intermediate portion. FIG. 図2は本発明の鉛蓄電池用極板の実施形態1の模式図である。FIG. 2 is a schematic diagram of Embodiment 1 of the electrode plate for a lead storage battery of the present invention. 図3は本発明の鉛蓄電池用極板の実施形態2の模式図である。FIG. 3 is a schematic diagram of Embodiment 2 of the electrode plate for a lead storage battery of the present invention. 図4(a)は本発明の実施形態1の電池用極板の斜視模式図であり、図4(b)は図4(a)に示す電池用極板の正面図であり、図4(c)は図4(a)に示す電池用極板の横断面図である。4A is a schematic perspective view of the battery electrode plate according to the first embodiment of the present invention, and FIG. 4B is a front view of the battery electrode plate shown in FIG. 4A. c) is a cross-sectional view of the battery electrode plate shown in FIG. 図5(a)はエキスバンド法でエキスバンド格子及び極板を製造するための工程図であり、図5(b)は上記工程の局部拡大模式図である。FIG. 5 (a) is a process diagram for manufacturing the extended grating and the electrode plate by the extended method, and FIG. 5 (b) is a partially enlarged schematic view of the above process.
 以下、本発明の実施形態を図面に基づいて説明する。図面において、簡単のため、機能が実質的に同一の構成要件について同一の符号を付する。なお、本発明は以下の実施形態に限られるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In the drawings, for the sake of simplicity, components having substantially the same functions are denoted by the same reference numerals. The present invention is not limited to the following embodiment.
 本発明は、複数のセル電池を有する鉛蓄電池を提供する。該鉛蓄電池は、極板群、電解液及びセル電池チャンバーを有する複数のセル電池を有し、前記極板群及び前記電解液は前記セル電池チャンバーに収容され、前記極板群は複数の正極板及び複数の負極板がセパレータを介して交互に配列したものであり、前記正極板は、正極極耳を有する正極集電体と該正極集電体によって保持された正極活物質層とを備え、前記負極極耳を有する負極集電体と該負極集電体によって保持された負極活物質層とを備えている。前記セパレータはAGMセパレータであり、前記極板群及び前記電解液が前記セル電池チャンバーに収容され状態での前記セパレータの密度は117~129g/dmという範囲にあり、前記正極板及び前記負極板のうちの少なくとも1つの極板は以下の構造を有し、即ち、前記極板の集電体はエキスバンド法で作製したエキスバンド格子であり、前記極板は突起を有する両突起状端部と該両端部の間の平坦中間部分とを含み、前記端部の厚さが前記中間部分の厚さよりも大きく、前記中間部分の厚さをH2とし、前記端部の厚さと前記中間部分の厚さとの差をH1とした時に、H1とH2の比の値H1/H2は3%~9%である。上記端部の厚さは突起状端部の最大の厚さをいう。 The present invention provides a lead acid battery having a plurality of cell batteries. The lead storage battery includes a plurality of cell batteries having an electrode plate group, an electrolyte solution, and a cell battery chamber, the electrode plate group and the electrolyte solution are accommodated in the cell battery chamber, and the electrode plate group includes a plurality of positive electrodes. The positive electrode plate includes a positive electrode current collector having positive electrode ears, and a positive electrode active material layer held by the positive electrode current collector. And a negative electrode current collector having the negative electrode ear and a negative electrode active material layer held by the negative electrode current collector. The separator is an AGM separator, and the density of the separator in a state where the electrode group and the electrolytic solution are accommodated in the cell battery chamber is in a range of 117 to 129 g / dm 3 , and the positive electrode plate and the negative electrode plate At least one of the electrode plates has the following structure, that is, the current collector of the electrode plate is an extended grating produced by an extended method, and the electrode plate has both protruding end portions having protrusions. And a flat intermediate portion between the both end portions, 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 thickness of the end portion and the intermediate portion When the difference from the thickness is H1, the ratio H1 / H2 of H1 and H2 is 3% to 9%. The thickness of the end portion refers to the maximum thickness of the protruding end portion.
 本発明は、端部に突起が形成されることで極板の端部の厚さがその他の部分の厚さよりも大きくなるように極板を設計する。これにより、正極板と負極板との間隔が適宜に大きくなり、優れた容量、サイクル寿命、及び充電効率を同時に有する電池用極板を提供することができる。具体的には、まず、反応空間を大きくすることができ、より多くの硫酸を蓄積することができ、反応がより長く行うことができる。その結果、容量を向上することができる。次に、極板の両端部が厚く、両端部の格子裁断箇所のリブが極板の表面から遠く、セパレータを破れて短路することが困難である。と同時に、両端部の強度が大きいので、極板の成長を抑制する作用がある。その結果、サイクル寿命を向上することができる。さらに、両端部が厚いので、極板の中間部分とセパレータとの間に所定の隙間が生じ、充電時に酸素の搬送に有利で、酸素の同時不拡散及び酸素の損失による充電効率の低下を抑制することができる。その結果、充電効率を向上することができる。電池の通常充電時、電力の一部は硫酸鉛の反応に、もう一部は水の分解にそれぞれ用いられる。酸素がリアルタイムに負極に搬送できないと、堆積が生じやすくなる。その結果として、その1.硫酸鉛の反応は酸素の堆積によって阻害される。その2. 酸素の堆積によって、酸素は負極までリアルタイムに拡散することができない。そのため、酸素の流失を導いてしまって、水が失う。上記二点はともに充電効率を低下する。ここでの充電効率は、硫酸鉛反応の難易度及び酸素循環の効率をいう。 In the present invention, the electrode plate is designed so that the thickness of the end portion of the electrode plate is larger than the thickness of the other portions by forming protrusions at the end portions. Thereby, the space | interval of a positive electrode plate and a negative electrode plate becomes large suitably, and the electrode plate for batteries which has the outstanding capacity | capacitance, cycle life, and charging efficiency simultaneously can be provided. Specifically, first, the reaction space can be increased, more sulfuric acid can be accumulated, and the reaction can be performed longer. As a result, the capacity can be improved. Next, both ends of the electrode plate are thick, and the ribs at the grid cutting portions on both ends are far from the surface of the electrode plate, and it is difficult to break the separator and make a short path. At the same time, the strength of both end portions is large, so that there is an action of suppressing the growth of the electrode plate. As a result, cycle life can be improved. In addition, because both ends are thick, a predetermined gap is created between the middle part of the electrode plate and the separator, which is advantageous for oxygen transport during charging, and suppresses reduction in charging efficiency due to simultaneous non-diffusion of oxygen and loss of oxygen. can do. As a result, charging efficiency can be improved. During normal charging of the battery, a part of the electric power is used for the reaction of lead sulfate and the other part is used for the decomposition of water. If oxygen cannot be transported to the negative electrode in real time, deposition tends to occur. As a result, The lead sulfate reaction is inhibited by oxygen deposition. No.2. O Due to the accumulation of oxygen, oxygen cannot diffuse to the negative electrode in real time. Therefore, it leads to the loss of oxygen and loses water. Both of the above two points lower the charging efficiency. The charging efficiency here refers to the difficulty of the lead sulfate reaction and the efficiency of oxygen circulation.
 一方、鉛蓄電池では、鉛蓄電池に優れたハイレート放電特性を持たせるために、上記極板群における隣り合う正極板と負極板との間隔が小さいことを要求されると考えられている。しかしながら、小さすぎると、樹枝状の結晶などの析出物は対向電極に到達しやすく、短絡するという不具合が生じる。また、上記正極板と負極板との間に配置されたセパレータに圧縮作用を発生し、電解液のセパレータにおける分布に対しても影響を与える。具体的には、上記正極板と負極板との間隔が小さすぎると、セパレータ層が過度に圧縮され、少量の電解液のみを維持することができるので、放電容量が低下する。上記正極板と負極板との間隔が大きくなると、上記正極板と負極板との間に配置されたセパレータは凹み、接触反応面積が減少し、放電容量が低下し、ハイレート放電特性が低下する。 On the other hand, it is considered that the lead storage battery is required to have a small interval between the positive electrode plate and the negative electrode plate adjacent to each other in order to give the lead storage battery excellent high rate discharge characteristics. However, if it is too small, precipitates such as dendritic crystals are likely to reach the counter electrode, resulting in a short circuit. In addition, the separator disposed between the positive electrode plate and the negative electrode plate generates a compressive action, which also affects the distribution of the electrolytic solution in the separator. Specifically, if the distance between the positive electrode plate and the negative electrode plate is too small, the separator layer is excessively compressed and only a small amount of the electrolyte can be maintained, so that the discharge capacity is reduced. When the gap between the positive electrode plate and the negative electrode plate is increased, the separator disposed between the positive electrode plate and the negative electrode plate is recessed, the contact reaction area is reduced, the discharge capacity is reduced, and the high rate discharge characteristics are reduced.
 しかし、以上のように、本発明の鉛蓄電池における上記正極板及び上記負極板のうちの少なくとも1つの極板は、両突起状端部を有し、かつ該両端部の厚さが中間部分の厚さよりも大きいため、上記正極板と負極板との間隔が大きくなり、結果として、サイクル寿命等などが向上するが、鉛蓄電池のハイレート放電容量を低下する可能性もある。これに対して、本願発明者は、より高い密度でセパレータを正極板と負極板との間に配置することで、鉛蓄電池に優れたハイレート放電特性を持たせることができることを発見した。そのため、本発明において、AGMセパレータを用い、該セパレータの密度を117~129g/dmという範囲に設定する。該密度の範囲が従来の鉛蓄電池のセパレータの密度よりも高いのは明らかである。さらに、本発明において、セパレータの密度の上限を129g/dmに設定しているのは、セパレータの密度がさらに高くなると、セパレータにおける電解液のサイクルに影響を与える可能性があり、電池のサイクル寿命にも影響する。 However, as described above, at least one of the positive electrode plate and the negative electrode plate in the lead storage battery of the present invention has both projecting end portions, and the thickness of the both end portions is an intermediate portion. Since it is larger than the thickness, the interval between the positive electrode plate and the negative electrode plate is increased, and as a result, the cycle life and the like are improved, but the high-rate discharge capacity of the lead storage battery may be reduced. On the other hand, this inventor discovered that the high-rate discharge characteristic which was excellent in the lead storage battery can be given by arrange | positioning a separator between a positive electrode plate and a negative electrode plate by higher density. Therefore, in the present invention, an AGM separator is used, and the density of the separator is set in a range of 117 to 129 g / dm 3 . It is clear that the density range is higher than the density of conventional lead-acid battery separators. Furthermore, in the present invention, the upper limit of the density of the separator is set to 129 g / dm 3 because if the separator density is further increased, the cycle of the electrolyte in the separator may be affected. It also affects the lifespan.
 本発明におけるセパレータの密度は、該セパレータ及び極板をプレスして極板群を形成する際に、117~129g/dmという高密度に圧縮したものであり、即ち、セパレータの密度は、極板群において受ける圧力に応じて決定されたものである。しかし、電池の化成の前後、セパレータの密度は基本的に変化しない。本発明において、セパレータの密度は化成後の密度をいう。 The density of the separator in the present invention is that which is compressed to a high density of 117 to 129 g / dm 3 when the separator and the electrode plate are pressed to form the electrode plate group. It is determined according to the pressure received in the plate group. However, the density of the separator basically does not change before and after the formation of the battery. In the present invention, the density of the separator refers to the density after chemical conversion.
 上記AGMセパレータが用いるガラス繊維セパレータの材料は、特に限定されるものではないが、公知又は市販の鉛蓄電池用AGMセパレータを用いてもよく、本発明の要求に満たせば良い。 The material of the glass fiber separator used by the AGM separator is not particularly limited, but a known or commercially available AGM separator for a lead storage battery may be used as long as it meets the requirements of the present invention.
 上記対向極板及びセパレータの構造及び組成の設定に基づいて、本発明は、密度の低い電解液を用いてもよく、液注入時の電解液の密度は1.24~1.26g/cmであることが好ましく、上記鉛蓄電池化成後の上記電解液の密度は1.33~1.35g/cmであることが好ましい。鉛蓄電池は、一定時間の使用後、該鉛蓄電池を満充電した後、その電解液の密度が依然として上記鉛蓄電池化成後の上記電解液の密度に復帰することができるため、本発明において、特別な説明がない限り、上記電解液の密度は、上記鉛蓄電池化成後の上記電解液の密度をいう。該電解液は硫酸と水とを含む硫酸水溶液であることが好ましい。上記電解液には、例えば、二酸化シリコン、四ホウ酸ナトリウム、硫酸ナトリウムなどの、該電解液に完全に溶解できる添加剤を少量加えてもよい。上記電解液における上記添加剤の含有量は例えば0.2~1.0wt%である。 Based on the setting of the structure and composition of the counter electrode plate and the separator, the present invention may use a low density electrolytic solution, and the density of the electrolytic solution at the time of liquid injection is 1.24 to 1.26 g / cm 3. The density of the electrolytic solution after the formation of the lead storage battery is preferably 1.33 to 1.35 g / cm 3 . In the present invention, the lead-acid battery can be restored to the density of the electrolyte after the formation of the lead-acid battery after the lead-acid battery is fully charged after a certain period of use. Unless otherwise explained, the density of the electrolytic solution refers to the density of the electrolytic solution after the formation of the lead storage battery. The electrolytic solution is preferably an aqueous sulfuric acid solution containing sulfuric acid and water. A small amount of an additive that can be completely dissolved in the electrolytic solution, such as silicon dioxide, sodium tetraborate, and sodium sulfate, may be added to the electrolytic solution. The content of the additive in the electrolytic solution is, for example, 0.2 to 1.0 wt%.
 鉛蓄電池では、電解液としての硫酸水溶液の比重が高くなると、硫酸及び鉛との間の化学反応が活発になり、鉛が析出しにくいため、電池の容量が向上する。一方、電解液としての硫酸水溶液の比重が高くなると、硫酸の粘度が大きすぎて、セパレータにおける電解液のサイクルに影響を与え、セパレータに付着した硫酸も下向きに流れ又は下向きに沈殿するため、硫酸が分層しやすくなる。その結果、電池のサイクル寿命に影響する。 In a lead-acid battery, when the specific gravity of the sulfuric acid aqueous solution as the electrolytic solution increases, a chemical reaction between sulfuric acid and lead becomes active, and lead does not easily precipitate, so that the capacity of the battery is improved. On the other hand, if the specific gravity of the sulfuric acid aqueous solution as the electrolytic solution is increased, the viscosity of the sulfuric acid is too large, which affects the cycle of the electrolytic solution in the separator, and the sulfuric acid adhering to the separator also flows downward or precipitates downward. Becomes easier to separate layers. As a result, the cycle life of the battery is affected.
 本発明において、上記セパレータ及び上記密度の電解液を用いた結果、電池のサイクル寿命、充放電効率、放電容量及びハイレート放電容量はともに良くなることを発見した。 In the present invention, as a result of using the separator and the electrolytic solution having the above density, it has been found that the cycle life, charge / discharge efficiency, discharge capacity and high rate discharge capacity of the battery are all improved.
 本発明の鉛蓄電池は弁制御式の鉛蓄電池であることが好ましい。 The lead storage battery of the present invention is preferably a valve-controlled lead storage battery.
 図1は、本発明の鉛蓄電池における高密度AGMセパレータと両突起状端部を有しかつ該両端部の厚さが中間部分の厚さよりも大きい極板を用いた極板群を模式的に示す図である。図1に示すのは両端部に突起が形成された負極板であるが、後述のように、実際、本発明において正極板の両端部に突起が形成されることが好ましい。ただし、図1に示す極板群では、正極板がセパレータに覆われ、見えにくいため、外に露出した負極板で模式的に示している。負極板の両端部に突起が形成された状態と正極板の両端部に突起が形成された状態とは同様である。 FIG. 1 schematically shows an electrode plate group using a high-density AGM separator and electrode plates having both protruding end portions in the lead storage battery of the present invention and having both end portions larger in thickness than the intermediate portion. FIG. Although FIG. 1 shows a negative electrode plate having protrusions at both ends, it is preferable that protrusions are actually formed at both ends of the positive electrode plate in the present invention, as will be described later. However, in the electrode group shown in FIG. 1, since the positive electrode plate is covered with the separator and is difficult to see, it is schematically shown by the negative electrode plate exposed to the outside. The state in which the protrusions are formed on both ends of the negative electrode plate is the same as the state in which the protrusions are formed on both ends of the positive electrode plate.
 図2は本発明の鉛蓄電池用極板の実施形態1の模式図である。図2に示すように、上記極板の中間部分の厚さをH2とし、上記極板の端部の厚さと中間部分の厚さとの差をH1とし、上記極板の端部の幅をH3とし、上記極板の全幅はH4とする。図2において、上記両突起状端部のそれぞれが有する突起は、上記極板の同一側に形成され、後述の裁断工程でホッビング方式で裁断することで形成することが好ましい。 FIG. 2 is a schematic diagram of Embodiment 1 of the electrode plate for a lead storage battery of the present invention. As shown in FIG. 2, 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, and the width of the end portion of the electrode plate is H3. And the total width of the electrode plate is H4. In FIG. 2, it is preferable that the protrusions of the both protruding end portions are formed on the same side of the electrode plate and are cut by a hobbing method in a cutting process described later.
 図3は本発明の鉛蓄電池用極板の実施形態2の模式図である。図3に示すように、上記両突起状端部のそれぞれが有する突起の形状は図1に示したものとは異なり、また、両突起状端部のそれぞれが有する突起は、上記極板の異なる側に形成され、後述の裁断工程に用いられるプレス方式で裁断して形成することが好ましい。 FIG. 3 is a schematic diagram of Embodiment 2 of the electrode plate for a lead storage battery of the present invention. As shown in FIG. 3, the shape of the protrusions of each of the two protruding ends is different from that shown in FIG. 1, and the protrusion of each of the protruding ends is different from that of the electrode plate. It is preferable to form by cutting by the press method formed in the side and used for the cutting process mentioned later.
 図4(a)は本発明の実施形態1の電池用極板の斜視模式図であり、図4(b)は図4(a)に示す電池用極板の正面図であり、図4(c)は図4(a)に示す電池用極板の横断面図である。 4A is a schematic perspective view of the battery electrode plate according to the first embodiment of the present invention, and FIG. 4B is a front view of the battery electrode plate shown in FIG. 4A. c) is a cross-sectional view of the battery electrode plate shown in FIG.
 図4(a)、(b)、(c)に示すように、上記極板は、突起を有する両突起状端部と該両端部の間の平坦な中間部分とからなり、上記端部の厚さは上記中間部分の厚さよりも大きい。両突起状端部が有する突起は、集電体及び/又は該集電体に保持された活物質層によって形成されても良いが、プロセスの簡易化、コストの低減化のことを考えると、上記突起は活物質層のみによって形成されることが好ましい。 As shown in FIGS. 4 (a), (b), and (c), the electrode plate is composed of both protruding end portions having protrusions and flat intermediate portions between the both end portions. The thickness is greater than the thickness of the intermediate portion. The protrusions of both protruding ends may be formed by a current collector and / or an active material layer held by the current collector, but considering the simplification of the process and the reduction of cost, The protrusion is preferably formed only by the active material layer.
 上記突起の厚さは上記の厚さの差H1であり、該H1が所定範囲に入らなければ、セパレータ及び極板との間に適切な隙間を形成することができない。そのため、充電効率を高めることができ、短絡を防止することができ、サイクル寿命及び容量を高めることができる。しかし、H1が大きすぎると、両端部の活物質が過度に突起し、かえって短絡のリスクが大きくなる。同時に、極板間の隙間が大きすぎて、電池の水がなくなるのを加速し、逆効果が生じてしまう。一方、H1が小さすぎると、両端部と中間部分との厚さの差が明らかではなく、効率的に充電効率を向上することができない。また、極板の成長を抑制する効果も明らかではない。そのため、上記2点から考えると、H1とH2との比の値H1/H2は3%~9%となる。さらに、比の値H1/H2が0である場合と比較して、比の値H1/H2が3%~9%である場合は、電池の容量は約10%~20%高くなる。より良い効果を奏する点から考えると、比の値H1/H2は4%~8%であることがより好ましい。 The thickness of the protrusion is the thickness difference H1, and if the H1 does not fall within a predetermined range, an appropriate gap cannot be formed between the separator and the electrode plate. Therefore, charging efficiency can be increased, short circuit can be prevented, and cycle life and capacity can be increased. However, if H1 is too large, the active materials at both ends protrude excessively, and on the contrary, the risk of a short circuit increases. At the same time, the gap between the electrode plates is too large, accelerating the loss of water in the battery, resulting in an adverse effect. On the other hand, if H1 is too small, the difference in thickness between the both end portions and the intermediate portion is not clear, and the charging efficiency cannot be improved efficiently. Further, the effect of suppressing the growth of the electrode plate is not clear. Therefore, considering the above two points, the ratio value H1 / H2 of H1 and H2 is 3% to 9%. Further, when the ratio value H1 / H2 is 3% to 9%, the capacity of the battery is about 10% to 20% higher than when the ratio value H1 / H2 is 0. From the viewpoint of better effects, the ratio value H1 / H2 is more preferably 4% to 8%.
 なお、上記突起の形状は、特に限定されるものではないが、突起状端部を形成することができればよく、例えば、ドーム状、山峰状などであってもよい。上記突起の厚さは、突起の頂点における最大の厚さをいう。 Note that the shape of the protrusion is not particularly limited, but may be a dome shape, a mountain peak shape, or the like as long as it can form a protruding end. The thickness of the protrusion refers to the maximum thickness at the apex of the protrusion.
 上記突起の幅は、上記極板の端部の幅H3である。該H3が大きすぎると、生産は困難となり、セパレータと極板との間の隙間が大きすぎる。よって、極板群における活物質の膨張を有効的に防止することができず、活物質の脱落をも防止することもできない。そのため、電池のサイクル寿命が悪くなる。一方、該H3が小さすぎると、極板の両端部の応力が低すぎて、極板の成長を有効的に抑制することができないため、電池の容量が不安定となり、サイクル寿命が悪くなる。よって、上記の2点から考えると、比の値H3/H4は5%~25%であることが好ましく、10%~20%であることがより好ましい。 The width of the protrusion is the width H3 of the end of the electrode plate. If the H3 is too large, production becomes difficult, and the gap between the separator and the electrode plate is too large. Therefore, the expansion of the active material in the electrode plate group cannot be effectively prevented, and the active material cannot be prevented from falling off. Therefore, the cycle life of the battery is deteriorated. On the other hand, if the H3 is too small, the stress at both ends of the electrode plate is too low to suppress the growth of the electrode plate effectively, resulting in unstable battery capacity and poor cycle life. Therefore, considering the above two points, the ratio value H3 / H4 is preferably 5% to 25%, and more preferably 10% to 20%.
 上記極板は正極板であってもよく、負極板であってもよいが、正極板であることが好ましい。これは、鉛蓄電池において、正極がガスを生成し、正極板の格子が成長しやすく、短路が発生しやすいためである。また、電池の容量は正極によって制御されるので、負極板と比較して、正極板に上記突起を形成する場合、効果をより良く奏することができる。 The electrode plate may be a positive electrode plate or a negative electrode plate, but is preferably a positive electrode plate. This is because in a lead-acid battery, the positive electrode generates gas, the grid of the positive electrode plate is likely to grow, and short paths are likely to occur. Further, since the capacity of the battery is controlled by the positive electrode, the effect can be further improved when the protrusion is formed on the positive electrode plate as compared with the negative electrode plate.
 上記両突起状端部のそれぞれが有する突起は、上記極板の同一側に形成されてもよく、異なる側に形成されてもよいが、前者が好ましい。これは、上記両突起が極板の同一側に形成された状態で生じた隙間は上記両突起が極板の異なる側に形成された状態で生じた隙間よりも大きく、より多くの硫酸を蓄積することができ、電池の容量を高めることができる。また、当該状態の極板で電池の充電効率を高めることができるとともに、電池寿命の早期失効に対しても著しい抑制効果がある。よって、得られた極板群及び該極板群を用いた電池の性能、効果はさらに良くなる。 The projections of each of the two projecting ends may be formed on the same side of the electrode plate or may be formed on different sides, but the former is preferable. This is because the gap formed when both protrusions are formed on the same side of the electrode plate is larger than the gap generated when both protrusions are formed on different sides of the electrode plate, and more sulfuric acid is accumulated. Battery capacity can be increased. In addition, the electrode plate in this state can increase the charging efficiency of the battery, and has a remarkable suppression effect on the early expiration of the battery life. Therefore, the performance and effect of the obtained electrode plate group and the battery using the electrode plate group are further improved.
 上記突起は、上記極板の製造方法のプロセス条件を設計することで形成することができ、活物質層の構成を設計することで形成することもできる。 The protrusion can be formed by designing the process conditions of the method for manufacturing the electrode plate, and can also be formed by designing the configuration of the active material layer.
 図5(a)及び図5(b)には、極板の製造方法における主要な工程を示す。(1)往復動式プレス金型を用いて鉛又は鉛合金によって形成された鉛帯27に対しプレスを繰り返し行い、鉛帯27の長さ方向に沿って複数のスリットを形成すると共に、該スリットを鉛帯の表面に直交する方向に広げることにより、複数の格子線が交差してなるメッシュ25を有する格子状シートを形成するエキスパンド加工工程と、(2)整形用金型の一対のローラを用いて前記格子状シートを整形し、エキスパンド格子を得る整形工程と、(3)エキスパンド格子に、その長さ方向に沿って活物質としての鉛ペースト24aを充填して鉛板を形成する鉛ペースト充填工程と、(4)鉛ペースト24aが充填されたエキスパンド格子を、極耳9を有する正極板となるように裁断する裁断工程とを備えることで、未化成の極板2aを得る。 FIG. 5 (a) and FIG. 5 (b) show main steps in the electrode plate manufacturing method. (1) Using a reciprocating press mold, pressing is repeatedly performed on the lead strip 27 formed of lead or a lead alloy to form a plurality of slits along the length direction of the lead strip 27, and the slits Expanding in a direction perpendicular to the surface of the lead strip, and an expanding process for forming a grid-like sheet having a mesh 25 in which a plurality of grid lines intersect, and (2) a pair of rollers of the shaping mold A shaping step of shaping the lattice sheet to obtain an expanded lattice, and (3) a lead paste for forming a lead plate by filling the expanded lattice with a lead paste 24a as an active material along its length direction. An unformed electrode plate 2a is obtained by including a filling step and (4) a cutting step of cutting the expanded lattice filled with the lead paste 24a into a positive electrode plate having the polar ears 9.
 その後、未化成の極板2aを硬化、乾燥、化成して極板を得る。化成は、未化成の正極板及び負極板で極板群を作製して鉛蓄電池の電槽に装着した後に行ってもよく、極板群を作製する前に行ってもよいが、前者が好ましい。 Thereafter, the unformed electrode plate 2a is cured, dried and formed to obtain the electrode plate. Chemical conversion may be performed after the electrode plate group is prepared with the unformed positive electrode plate and the negative electrode plate and attached to the battery case of the lead storage battery, or may be performed before the electrode plate group is manufactured, but the former is preferable. .
 なお、上記「厚さ」は全て電池製品を作製した後、使用されていない場合の各部分の厚さをいう。 Note that the above “thickness” refers to the thickness of each part when the battery product is not used after being manufactured.
 本発明に係る上記両突起状端部のそれぞれが有する突起は、上記裁断工程を行うと同時に形成されたものであり、即ち、上記裁断工程のプロセス条件を設計することで形成してもよい。具体的には、上記突起は、上記裁断工程においてホッビング方式で裁断して形成されてもよく、上記裁断工程においてプレス方式で裁断して形成されてもよい。ホッビング方式又はプレス方式で上記突起を形成する場合の具体的なプロセス及び利点欠点については、中国の特許出願であるCN102593430Aに記載の内容と全く同じであるため、該文献の関連する内容を参照する。 The projections of each of the two projecting ends according to the present invention are formed simultaneously with the cutting step, that is, may be formed by designing the process conditions of the cutting step. Specifically, the protrusion may be formed by cutting with a hobbing method in the cutting step, or may be formed by cutting with a press method in the cutting step. The specific process and advantages and disadvantages of forming the protrusions by the hobbing method or the pressing method are exactly the same as those described in CN10593430A, which is a Chinese patent application, so refer to the related contents of the document. .
 本発明では、ホッビング方式及びプレス方式のうちのホッビング方式がより好ましい。 In the present invention, the hobbing method of the hobbing method and the press method is more preferable.
 本発明では、両端部の活物質の強度を高めることで、極板を裁断するときに極板の両端部に形成された突起の保持を実現することができる。即ち、活物質の密度を高めることで実現することができる。このように、極板を裁断した後、両端部の厚い状態を保持することができる。この点を考慮すると、上記活物質層の密度である鉛ペースト密度は4.15g/cm~5.0g/cmであることが好ましく、4.25g/cm~4.8g/cmであることがより好ましい。上記範囲の鉛ペースト密度は通常の鉛ペーストの密度よりも高い。しかし、正極板及び負極板にとっては、各自の鉛ペーストの組成は異なり、上記突起を形成するための鉛ペーストの密度も異なる。つまり、正極板及び負極板の鉛ペーストの組成が異なるため、両方の鉛ペーストの密度が同じであっても、同じ裁断方法で裁断した後、突起はある程度異なる。また、負極板の鉛ペーストは、実際に要求される特性に応じて、その組成成分の割合を大きく変化する必要がある。そのため、その鉛ペーストの密度が同じであっても、その組成成分の割合が異なると、突起はある程度異なる。よって、上記極板は正極板であることが好ましく、該正極板の鉛ペースト密度は4.15g/cm~4.45g/cmであることが好ましく、4.25g/cm~4.35g/cmであることがより好ましい。 In the present invention, by increasing the strength of the active material at both ends, it is possible to realize the retention of the protrusions formed at both ends of the electrode plate when the electrode plate is cut. That is, it can be realized by increasing the density of the active material. Thus, after cutting an electrode plate, the thick state of both ends can be maintained. From this viewpoint, it is preferable that lead paste density is the density of the active material layer is 4.15g / cm 3 ~ 5.0g / cm 3, 4.25g / cm 3 ~ 4.8g / cm 3 It is more preferable that The lead paste density in the above range is higher than that of normal lead paste. However, the composition of the lead paste for each of the positive electrode plate and the negative electrode plate is different, and the density of the lead paste for forming the protrusions is also different. That is, since the composition of the lead paste of the positive electrode plate and that of the negative electrode plate are different, even if both lead pastes have the same density, the protrusions are somewhat different after being cut by the same cutting method. Moreover, the lead paste of a negative electrode plate needs to change the ratio of the composition component largely according to the characteristic actually requested | required. Therefore, even if the density of the lead paste is the same, the protrusions differ to some extent if the proportions of the composition components are different. Therefore, it is preferable that the electrode plate is a positive electrode plate, preferably of lead paste density of the positive electrode plate is 4.15g / cm 3 ~ 4.45g / cm 3, 4.25g / cm 3 ~ 4. More preferably, it is 35 g / cm 3 .
 しかし、同じ鉛ペーストの密度の下、裁断プロセス及び裁断カッターのブレード角度などの調整によって上記突起の形状、大きさ及び高さの制御を実現することができ、この点の内容は中国特許出願であるCN102593430A を参照する。 However, the shape, size and height of the protrusion can be controlled by adjusting the cutting process and blade angle of the cutting cutter under the same lead paste density. Reference is made to a certain CN102593430A.
 本発明の鉛蓄電池では、上記部材の構造及び組成以外、その他の部材の構造及び組成は、従来技術のものを採用し、特に限定されるものではない。 In the lead storage battery of the present invention, other than the structure and composition of the above members, the structure and composition of other members adopt those of the prior art and are not particularly limited.
 例えば、上記鉛蓄電池は下記の方法で組み立てることができる。複数の上記正極板及び上記負極板をセパレータ構造体を介して交互に重なり合うことで、極板群が得られる。その後、鉛、アルミニウム又は銅材などの金属板を用いて単一の極板群における同極性の正極極耳を溶接又は鋳込み溶接することで正極バスが得られる。一方、鉛、アルミニウム又は銅材などの金属板を用いて単一の極板群における同極性の負極極耳を溶接又は鋳込み溶接することで負極バスが得られる。各極板群が電槽における区画壁によって区画された複数のセル電池チャンバーに収容される。鉛、アルミニウム又は銅材などの金属板を用いて、極板群の負極バスと隣り合うセル電池の極板群の正極バスを溶接し、その後、鉛、アルミニウム又は銅材などの金属板を用いて、上記隣り合うセル電池の極板群の負極バス又は次の隣り合うセル電池の極板群の正極バスを溶接する。このように直列にしていくと、各極板群が直列に接続される。即ち、複数のセル電池を直列に接続することで、最終的に両端の正極バス及び負極バスはそれぞれ正極端及び負極端になる。上記正極端を正極端子に接続し、上記負極端を負極端子に接続する。 For example, the lead storage battery can be assembled by the following method. A plurality of the positive plates and the negative plates are alternately overlapped with each other through the separator structure to obtain an electrode plate group. Then, a positive electrode bus is obtained by welding or casting welding the positive electrode ears of the same polarity in a single electrode plate group using a metal plate such as lead, aluminum or copper. On the other hand, a negative electrode bus is obtained by welding or casting welding the negative electrode ears of the same polarity in a single electrode plate group using a metal plate such as lead, aluminum or copper. Each electrode plate group is accommodated in a plurality of cell battery chambers partitioned by partition walls in the battery case. Using a metal plate such as lead, aluminum or copper, weld the negative electrode bus of the electrode plate group and the positive electrode bus of the electrode plate group of the adjacent cell battery, and then use a metal plate such as lead, aluminum or copper material Then, the negative electrode bus of the electrode plate group of the adjacent cell batteries or the positive electrode bus of the electrode plate group of the next adjacent cell battery is welded. In this way, each electrode plate group is connected in series. That is, by connecting a plurality of cell batteries in series, the positive electrode bus and the negative electrode bus at both ends finally 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.
 その後、電池蓋を電槽の開口に取付ける。その後、電池蓋に設けられた液注入口から各セル電池に電解液を注入し、電槽において化成を行う。液注入時の電解液の密度は1.24~1.26g/cmであることが好ましく、上記鉛蓄電池化成後の上記電解液の密度は1.33~1.35g/cmであることが好ましい。上記電解液に二酸化シリコンなどの添加物が含まれてもよい。化成後、電池内部において生成したガスと圧力を排出する弁を液注入口に固定することで、鉛蓄電池が得られる。 Thereafter, the battery cover is attached to the opening of the battery case. Then, electrolyte solution is inject | poured into each cell battery from the liquid injection port provided in the battery cover, and it forms in a battery case. The density of the electrolytic solution at the time of liquid injection is preferably 1.24 to 1.26 g / cm 3 , and the density of the electrolytic solution after the formation of the lead storage battery is 1.33 to 1.35 g / cm 3. Is preferred. The electrolyte solution may contain an additive such as silicon dioxide. After the formation, a lead storage battery is obtained by fixing the gas generated in the battery and a valve for discharging the pressure to the liquid inlet.
 以下、実施例に基づいて本発明を具体的に説明するが、これらの実施例は本発明の例示に過ぎず、本発明を限定するものではない。 Hereinafter, the present invention will be described in detail based on examples, but these examples are merely illustrative of the present invention and do not limit the present invention.
 (実施例C)
(1)正極板の製造
 約100:12:14の比重比で原材料である鉛粉(鉛と酸化鉛との混合物)と、水と、希硫酸とを混合することで、正極活物質としての正極鉛ペーストを得る。
(Example C)
(1) Manufacture of positive electrode plate By mixing lead powder (mixture of lead and lead oxide), water, and dilute sulfuric acid as raw materials at a specific gravity ratio of about 100: 12: 14, A positive lead paste is obtained.
 一方、注湯で得られた、約0.07質量%のCa及び約1.3質量%のSnを含むPb合金の鉛帯が1.3mmの厚さとなるように押し出す。図5(a)及び図5(b)に示すように、エキスパンド加工工程を行い、往復動式プレス金型を用いて鉛帯27に対しプレスを繰り返し行い、鉛帯27の長さ方向に沿って複数のスリットを形成すると共に、該スリットを鉛帯の表面に直交する方向に広げることにより、複数の格子線が交差してなるメッシュ25を有する格子状シートを形成する。その後、整形用金型の一対のローラを用いて前記格子状シートを整形し、エキスパンド格子を得る。その後、エキスパンド格子25に、その長さ方向に沿って活物質としての鉛ペースト24aを充填して鉛板2を形成する。その後、正極極耳9を有する正極板となるようにホッビング方式で鉛板2を裁断し、該正極板の同一側の両端部に突起を形成する。このように裁断した正極板を硬化、乾燥、化成して、正極板格子で正極活物質を保持した正極板を得る。上記化成は、極板群に組み立てる前に行ってもよく、極板群に組み立て鉛蓄電池の電槽に装着した後に行ってもよい。 Meanwhile, the Pb alloy lead band containing about 0.07 mass% Ca and about 1.3 mass% Sn obtained by pouring is extruded so as to have a thickness of 1.3 mm. As shown in FIG. 5A and FIG. 5B, the expanding process is performed, the press is repeatedly performed on the lead band 27 using a reciprocating press mold, and the length of the lead band 27 is increased. A plurality of slits are formed, and the slits are widened in a direction perpendicular to the surface of the lead strip, thereby forming a lattice-like sheet having a mesh 25 in which a plurality of lattice lines intersect. Thereafter, the lattice sheet is shaped using a pair of rollers of a shaping mold to obtain an expanded lattice. Thereafter, the expanded lattice 25 is filled with a lead paste 24a as an active material along the length direction to form the lead plate 2. Thereafter, the lead plate 2 is cut by a hobbing method so that the positive electrode plate having the positive electrode ears 9 is formed, and protrusions are formed at both ends on the same side of the positive electrode plate. The positive electrode plate thus cut is cured, dried, and formed to obtain a positive electrode plate that holds the positive electrode active material with a positive electrode plate lattice. The chemical conversion may be performed before assembling the electrode plate group, or may be performed after the electrode plate group is assembled and attached to the battery case of the lead storage battery.
 得られた正極板の各構成要素のパラメータは後述の表1に示す値を参照する。得られた突起の厚さの比の値H1/H2は3%であり、幅の比の値H3/H4は15%であり、得られた鉛ペーストの密度は4.3g/cmである。 For the parameters of each component of the obtained positive electrode plate, refer to values shown in Table 1 described later. The thickness ratio value H1 / H2 obtained is 3%, the width ratio value H3 / H4 is 15%, and the density of the obtained lead paste is 4.3 g / cm 3 . .
 (2)負極板の製造
 約100:10:4の比重比で原材料である鉛粉と、水と、希硫酸とを混合することで、正極活物質としての正極鉛ペーストを得る。
(2) Manufacture of Negative Electrode Plate A positive electrode lead paste as a positive electrode active material is obtained by mixing lead powder as a raw material, water, and dilute sulfuric acid at a specific gravity ratio of about 100: 10: 4.
 約0.07質量%のCa及び約0.25質量%のSnを含むPb合金の原料で、上記正極板と類似した往復動式エキスバンド法で負極集電体としての負極板エキスバンド格子を作製する。負極鉛ペーストで負極板のエキスバンド格子を充填する。その後、負極極耳を有する負極板となるようにホッビング方式で上記鉛ペーストが充填されたエキスバンド格子(鉛板)を裁断し、未化成の負極板を得る。未化成の負極板を硬化、乾燥、化成して、負極板格子で負極活物質を保持した負極板を得る。上記化成は、極板群に組み立てる前に行ってもよく、極板群に組み立て鉛蓄電池の電槽に装着した後に行ってもよい。 A Pb alloy raw material containing about 0.07% by mass of Ca and about 0.25% by mass of Sn. Make it. Fill the negative grid of the negative plate with negative lead paste. Thereafter, the expanded lattice (lead plate) filled with the above-mentioned lead paste is cut by a hobbing method so as to be a negative electrode plate having negative electrode ears, thereby obtaining an unformed negative electrode plate. The unformed negative electrode plate is cured, dried and formed to obtain a negative electrode plate in which the negative electrode active material is held by the negative electrode plate lattice. The chemical conversion may be performed before assembling the electrode plate group, or may be performed after the electrode plate group is assembled and attached to the battery case of the lead storage battery.
 得られた負極板の各構成要素のパラメータは後述の表1に示す値を参照する。得られた負極板の表面が平坦で、厚さが均一で、該負極板の端部に突起が形成されていないため、端部の厚さの比の値H1/H2は0であり、幅の比の値H3/H4は0である。得られた負極板の鉛ペースト密度は4.8g/cmである。 For the parameters of each component of the obtained negative electrode plate, refer to values shown in Table 1 described later. Since the surface of the obtained negative electrode plate is flat, the thickness is uniform, and no protrusion is formed at the end of the negative electrode plate, the ratio H1 / H2 of the thickness of the end is 0 and the width The ratio value H3 / H4 is zero. The lead paste density of the obtained negative electrode plate is 4.8 g / cm 3 .
 (3)鉛蓄電池の製造
 複数の上記正極板及び複数の上記負極板は、それぞれ密度が123g/dmであるAGMセパレータを介して交互に重なり合うことで、極板群を得る。得られた単一の極板群における同極性の正極極耳を溶接して正極バスを得る。一方、同極性の負極極耳を溶接してバスを得る。6つの極板群は、電槽における区画壁で区画された6つのセル電池チャンバーにそれぞれ収容されている。極板群の負極バスと隣り合う極板群的正極バスとを溶接することで、隣り合う2つの極板群を直列に接続する。各極板群を順に直列に接続する、即ち、各セル電池を直列に接続する。
(3) Manufacture of lead acid battery A plurality of said positive electrode plates and a plurality of said negative electrode plates overlap each other through AGM separators each having a density of 123 g / dm 3 to obtain an electrode plate group. The positive electrode ears of the same polarity in the obtained single electrode plate group are welded to obtain a positive electrode bus. On the other hand, a negative electrode ear with the same polarity is welded to obtain a bath. The six electrode plate groups are respectively accommodated in six cell battery chambers partitioned by partition walls in the battery case. By welding the negative electrode bus of the electrode plate group and the adjacent electrode plate group positive electrode bus, two adjacent electrode plate groups are connected in series. Each electrode plate group is connected in series, that is, each cell battery is connected in series.
 上記複数の直列に接続された極板群において、最終の両端に位置する両極板群のうちの一方の正極バスを正極端子に接続し、他方の負極バスを負極端子に接続する。その後、電池蓋を電槽の開口に取付ける。その後、濃度が1.242g/cmの硫酸を電解液として、電池蓋に設けられた液注入口から各セル電池に注入し、電槽で化成を行う。上記化成後、上記電解液の密度は1.34g/cmとなる。化成後、電池内部において生成したガスと圧力を排出する弁を液注入口に固定することで、鉛蓄電池が得られる。該電池の容量は100Ahであり、定格電圧は12Vである。 In the plurality of series-connected electrode plate groups, one positive electrode bus of the two electrode plate groups positioned at both ends is connected to the positive electrode terminal, and the other negative electrode bus is connected to the negative electrode terminal. Thereafter, the battery cover is attached to the opening of the battery case. Thereafter, sulfuric acid having a concentration of 1.242 g / cm 3 is injected as an electrolytic solution into each cell battery from a liquid inlet provided in the battery lid, and chemical conversion is performed in the battery case. After the chemical conversion, the density of the electrolytic solution is 1.34 g / cm 3 . After the formation, a lead storage battery is obtained by fixing the gas generated in the battery and a valve for discharging the pressure to the liquid inlet. The battery has a capacity of 100 Ah and a rated voltage of 12V.
 (4)鉛蓄電池の性能評価
 (A)上記得られた鉛蓄電池のサイクル寿命特性を測定し、得られた結果を後述の表1に示す。
(4) Performance evaluation of lead acid battery (A) The cycle life characteristic of the obtained lead acid battery was measured, and the obtained result is shown in Table 1 described later.
 サイクル寿命の測定方法は下記の通りである。 Measure method of cycle life is as follows.
 作製して30日以内の新品である電池に対して、電圧、内部抵抗及重量を測定した後、環境温度が25±2℃で、10.5Vまで25A放電終了後、該電池を満充電する。充電条件は14.7Vの定電圧で充電を行い、最大充電電流は40A以下である。このような充電ステップを終了後、当該充電ステップを第1回のサイクルとする。再び上記条件の下で放電と充電とを繰り返し行い、電池の放電容量が第1回のサイクルの放電容量の50%となる時点で試験を終了する。行われた充放電サイクルのサイクル数を算出して、該サイクル数をサイクル寿命とする。 After measuring the voltage, internal resistance, and weight of a battery that is new within 30 days after fabrication, the battery is fully charged after 25 A discharge to 10.5 V at an environmental temperature of 25 ± 2 ° C. . The charging is performed at a constant voltage of 14.7 V, and the maximum charging current is 40 A or less. After completing such a charging step, the charging step is defined as a first cycle. The discharge and charge are repeated again under the above conditions, and the test is terminated when the discharge capacity of the battery reaches 50% of the discharge capacity of the first cycle. The number of charge / discharge cycles performed is calculated, and the number of cycles is defined as the cycle life.
 (B)上記得られた鉛蓄電池の容量(電解液の反応効果)を測定し、得られた結果を後述の表1に示す。 (B) The capacity (reaction effect of the electrolytic solution) of the obtained lead storage battery was measured, and the obtained results are shown in Table 1 described later.
 電解液反応効果は電池の放電容量に反映され、電池の放電容量を測定することで電解液反応効果の良し悪しを表す。電池の容量の測定方法は下記の通りである。 The electrolyte reaction effect is reflected in the discharge capacity of the battery, and the measurement of the discharge capacity of the battery indicates whether the electrolyte reaction effect is good or bad. The method for measuring the capacity of the battery is as follows.
 作製して30日以内の新品である電池に対して、電圧、内部抵抗及重量を測定した後、環境温度が25±2℃で、10.5Vまで25A放電終了後、放電時間(単位は時間であり、hで記する)を記録し、電池の容量を算出する。 After measuring the voltage, internal resistance, and weight of a new battery within 30 days of fabrication, the environmental temperature is 25 ± 2 ° C., and after discharging 25 A to 10.5 V, the discharge time (unit is hours) And written in h), and the battery capacity is calculated.
 (C)上記得られた鉛蓄電池の充電効率(充電時間)を測定し、得られた結果を後述の表1に示す。 (C) The charging efficiency (charging time) of the obtained lead storage battery was measured, and the obtained results are shown in Table 1 described later.
 充電効率(充電時間)の測定方法は下記の通りである。 The method for measuring the charging efficiency (charging time) is as follows.
 25°Cで13.7Vの定電圧で充電を行う。充電電流が0.003倍定格容量以下となる場合、満充電と判定され、充電を終了する。充電を開始してから充電を終了するまでの時間を充電時間(単位は時間であり、hで記する)とする。一般的には、充電時間は短いほど充電効率が良い。 Charge at a constant voltage of 13.7V at 25 ° C. When the charging current is equal to or less than 0.003 times the rated capacity, it is determined that the battery is fully charged and the charging is terminated. The time from the start of charging to the end of charging is defined as the charging time (the unit is time, denoted by h). In general, the shorter the charging time, the better the charging efficiency.
 (D)上記得られた鉛蓄電池のハイレート放電特性を測定し、得られた結果を後述の表1に示す。 (D) The high-rate discharge characteristics of the obtained lead storage battery were measured, and the obtained results are shown in Table 1 described later.
 ハイレート放電特性はハイレート放電容量である。ハイレート放電容量の測定方法は下記の通りである。 The high rate discharge characteristic is the high rate discharge capacity. The method for measuring the high rate discharge capacity is as follows.
 作製して30日以内の新品である電池に対して、電圧、内部抵抗及重量を測定した後、環境温度が25±2℃で、9.6Vまで300A(3CA)放電終了後、放電時間(単位は時間であり、hで記する)を記録し、電池のハイレート放電容量を算出する。 After measuring the voltage, internal resistance, and weight of a new battery within 30 days of fabrication, the environmental temperature is 25 ± 2 ° C., and after the discharge of 300 A (3 CA) to 9.6 V, the discharge time ( The unit is time (denoted by h)), and the high rate discharge capacity of the battery is calculated.
 (実施例D~I)
 実施例D~Iにおいて、上記突起の厚さの比の値H1/H2を4%~9%という範囲のある数値とする以外、その他は実施例Cと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Examples D to I)
In Examples D to I, except for the ratio H1 / H2 of the ratio of the thickness of the protrusions to a value in the range of 4% to 9%, the electrode plate group and lead under the same installation conditions as Example C A storage battery was produced.
 (比較例A)
 比較例Aにおいて、正極板の鉛ペースト密度を4.2g/cmとし、正極板及び負極板には、ともに上記突起が形成されていない。即ち、比の値H1/H2及びH3/H4はともに0である。それ以外は、実施例Cと同様の設置及びプロセス方法で極板群及び鉛蓄電池を作製した。
(Comparative Example A)
In Comparative Example A, the lead paste density of the positive electrode plate was 4.2 g / cm 3, and neither of the protrusions was formed on the positive electrode plate and the negative electrode plate. That is, the ratio values H1 / H2 and H3 / H4 are both zero. Other than that, an electrode plate group and a lead storage battery were produced by the same installation and process method as in Example C.
 該比較例Aにおいて、正極板の鉛ペースト密度を実施例Cの4.3g/cmよりも低く設定したのは、突起を形成しないためである。しかし、裁断方式のプロセスの変更などで、正極板の鉛ペースト密度が4.3g/cmである場合でも、突起を形成しないことを実現することもできる。ただし、この場合は、生産性が低くなる。 In Comparative Example A, the lead paste density of the positive electrode plate was set lower than 4.3 g / cm 3 of Example C because no protrusion was formed. However, even if the lead paste density of the positive electrode plate is 4.3 g / cm 3 due to a change in the cutting process, it is possible to realize that no protrusion is formed. However, in this case, productivity is lowered.
 (比較例B、J)
 比較例B、Jにおいて、上記突起の厚さの比の値H1/H2をそれぞれ1%及び10%とした以外、その他は実施例Cと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Comparative Examples B and J)
In Comparative Examples B and J, an electrode plate group and a lead storage battery were produced under the same installation conditions as in Example C except that the thickness ratio values H1 / H2 of the protrusions were 1% and 10%, respectively. .
 表1に示すように、実施例C~Iで得られた結果から、上記突起の厚さの比の値H1/H2が3%~9%という範囲にある場合、得られた鉛蓄電池は、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に有していることが分かる。 As shown in Table 1, from the results obtained in Examples C to I, when the value H1 / H2 of the thickness ratio of the protrusions is in the range of 3% to 9%, the obtained lead storage battery is It can be seen that it has excellent cycle life, charge / discharge efficiency, discharge capacity and high rate discharge capacity at the same time.
 しかし、比較例A、B及びJで得られた結果から、当上記突起の厚さの比の値H1/H2が3%よりも低く又は9%を超えた場合、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に有効に実現することができない。その理由は以下のように考えられる。上記突起の厚さの比の値H1/H2が3%よりも低い場合、正極板と負極板との間隔が小さく、正極板と負極板とは近接しすぎた結果、以下の少なくとも一つの不具合を生じる可能性がある。短絡が発生し、酸素が負極に吸収されにくく、正極板と負極板との間の電解液が不足する。一方、上記突起の厚さの比の値H1/H2が10%よりも高い場合、正極板と負極板との間隔が大きすぎて、即ち、正極板と負極板との距離が大きすぎて、活物質が突出しすぎた結果、以下の少なくとも一つの不具合を生じる可能性がある。短絡が発生し、電池における水分の紛失量が増加し、電解液内部の抵抗が大きくなる。 However, from the results obtained in Comparative Examples A, B and J, when the ratio H1 / H2 of the thickness ratio of the protrusion is lower than 3% or exceeds 9%, excellent cycle life, charge / discharge Efficiency, discharge capacity and high rate discharge capacity cannot be effectively realized simultaneously. The reason is considered as follows. When the ratio H1 / H2 of the thickness ratio of the protrusion is lower than 3%, the distance between the positive electrode plate and the negative electrode plate is small, and the positive electrode plate and the negative electrode plate are too close to each other. May occur. A short circuit occurs, oxygen is hardly absorbed by the negative electrode, and the electrolyte solution between the positive electrode plate and the negative electrode plate is insufficient. On the other hand, when the ratio H1 / H2 of the thickness ratio of the protrusions is higher than 10%, the distance between the positive electrode plate and the negative electrode plate is too large, that is, the distance between the positive electrode plate and the negative electrode plate is too large, As a result of the active material protruding too much, at least one of the following problems may occur. A short circuit occurs, the amount of moisture lost in the battery increases, and the resistance inside the electrolyte increases.
 (実施例L~O)
 実施例L~Oにおいて、上記AGMセパレータの密度を117~129g/dmで変化する以外、その他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Examples L to O)
In Examples L to O, an electrode plate group and a lead storage battery were produced under the same installation conditions as Example F, except that the density of the AGM separator was changed from 117 to 129 g / dm 3 .
 (比較例K、P)
 比較例K、Pにおいて、上記AGMセパレータの密度をそれぞれ115 g/dm及び131g/dmとした以外、その他は、実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Comparative Examples K, P)
Comparative Example K, in P, except that the density of the AGM separators respectively 115 g / dm 3 and 131 g / dm 3, others, to prepare a plate group and lead-acid battery at the installation conditions as in Example F.
 表1に示すように,実施例L~Oで得られた結果から、上記AGMセパレータの密度を117~129g/dmという範囲にある場合、得られた鉛蓄電池は、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に有していることが分かる。 As shown in Table 1, from the results obtained in Examples L to O, when the density of the AGM separator is in the range of 117 to 129 g / dm 3 , the obtained lead storage battery has excellent cycle life and charge. It can be seen that the discharge efficiency, the discharge capacity, and the high rate discharge capacity are simultaneously provided.
 しかし、比較例K、Pで得られた結果から、上記AGMセパレータの密度が117g/dmよりも低く、又は129g/dmを超えた場合、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に実現することができないことが分かる。その理由は以下のように考えられる。上記AGMセパレータの密度が117g/dmよりも低い場合、セパレータにおける細孔が粗大過ぎて、毛細管現象が作用しなくなる。一方、上記AGMセパレータの密度が129g/dmを超えた場合、セパレータにおける細孔が少なすぎて、反応に参加する電解液が不足し、反応が低下する。 However, Comparative Example K, the results obtained with P, the density of the AGM separator is lower than 117 g / dm 3, or if it exceeds 129 g / dm 3, excellent cycle life, charge and discharge efficiency, discharge capacity and It can be seen that a high rate discharge capacity cannot be realized simultaneously. The reason is considered as follows. When the density of the AGM separator is lower than 117 g / dm 3 , the pores in the separator are too coarse and the capillary phenomenon does not work. On the other hand, when the density of the AGM separator exceeds 129 g / dm 3 , there are too few pores in the separator, the electrolyte solution participating in the reaction is insufficient, and the reaction is lowered.
 (実施例R~U)
 実施例R~Uにおいて、上記電解液の密度(上記鉛蓄電池の化成後の値)を1.33~1.35g/cmで変化する以外、その他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Examples R to U)
In Examples R to U, the density of the electrolytic solution (the value after the formation of the lead storage battery) was changed from 1.33 to 1.35 g / cm 3. A plate group and a lead-acid battery were produced.
 (比較例Q、V)
 比較例Q、Vにおいて、上記電解液の密度(上記鉛蓄電池の化成後の値)をそれぞれ1.32g/cm及び1.36g/cmとした以外、その他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Comparative Examples Q and V)
Comparative Example Q, the V, except that the density of the electrolyte solution (the value after conversion of the lead-acid battery), respectively 1.32 g / cm 3 and 1.36 g / cm 3, and other installation in the same manner as in Example F An electrode plate group and a lead storage battery were produced under the conditions.
 表1に示すように,実施例R~Uで得られた結果から、上記電解液の密度(上記鉛蓄電池の化成後の値)が1.33~1.35g/cmという範囲にある場合、得られた鉛蓄電池は、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に有していることが分かる。 As shown in Table 1, from the results obtained in Examples R to U, the density of the electrolytic solution (value after the formation of the lead storage battery) is in the range of 1.33 to 1.35 g / cm 3. It can be seen that the obtained lead storage battery has excellent cycle life, charge / discharge efficiency, discharge capacity and high rate discharge capacity at the same time.
 しかし、比較例Q、Vで得られた結果から、上記電解液の密度(上記鉛蓄電池の化成後の値)が1.33g/cmよりも低く、又は1.35g/cmを超えた場合、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に有効に実現することができないことが分かる。その理由は以下のように考えられる。上記電解液の密度(上記鉛蓄電池の化成後の値)が1.33g/cmよりも低い場合、反応に参加する硫酸塩が不足するため、反応が低下する。また、放電時、電解液が中性に近く、次に充電時に樹枝状の結晶の成長が発生しやすくなる。一方、上記電解液の密度(上記鉛蓄電池の化成後の値)が1.35g/cmを超えた場合、格子が腐食しやすく、イオンの移動抵抗が高くなる。 However, from the results obtained in Comparative Examples Q and V, the density of the electrolytic solution (value after the formation of the lead storage battery) was lower than 1.33 g / cm 3 or exceeded 1.35 g / cm 3 . In this case, it is understood that excellent cycle life, charge / discharge efficiency, discharge capacity, and high rate discharge capacity cannot be effectively realized simultaneously. The reason is considered as follows. When the density of the electrolytic solution (the value after the formation of the lead storage battery) is lower than 1.33 g / cm 3 , the reaction is lowered because the sulfate participating in the reaction is insufficient. In addition, the electrolyte is close to neutral during discharging, and dendritic crystal growth is likely to occur during charging. On the other hand, when the density of the electrolytic solution (the value after the formation of the lead storage battery) exceeds 1.35 g / cm 3 , the lattice is easily corroded and the ion migration resistance is increased.
 (比較例W)
 比較例Wにおいて、上記AGMセパレータの密度を114g/dmとし、上記電解液の密度(上記鉛蓄電池の化成後の値)を1.31g/cmとした以外、その他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Comparative Example W)
In Comparative Example W, the density of the AGM separator was 114 g / dm 3, and the density of the electrolytic solution (value after the formation of the lead storage battery) was 1.31 g / cm 3. The electrode plate group and the lead storage battery were produced under the installation conditions of
 比較例Wにおいて、上記AGMセパレータの密度及び上記電解液の密度はともに本発明的範囲に存在しない。これは、本発明の従来技術である中国特許出願のCN102593430Aにおける上記技術に相当する一例である。 In Comparative Example W, the density of the AGM separator and the density of the electrolytic solution are not within the scope of the present invention. This is an example corresponding to the above-described technique in CN10259430A of the Chinese patent application which is the prior art of the present invention.
 表1に示すように,実施例F等と比較して、比較例Wの電池の総合性能が本発明と異なるのは明らかであり、優れたサイクル寿命、充放電効率、放電容量及びハイレート放電容量を同時に実現することができない。 As shown in Table 1, it is clear that the overall performance of the battery of Comparative Example W is different from that of the present invention compared to Example F and the like, and excellent cycle life, charge / discharge efficiency, discharge capacity, and high rate discharge capacity. Cannot be realized at the same time.
 (実施例X)
 実施例Xにおいて、負極板の両端部に突起が形成され、上記突起の厚さの比の値H1/H2は6%であり、幅の比の値H3/H4は15%である。正極板の表面が平坦で、厚さが均一で、該正極板の端部に突起が形成されず、即ち、該正極板の端部の厚さの比の値H1/H2は0であり、幅の比の値H3/H4は0である。それ以外、その他はその他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Example X)
In Example X, protrusions are formed at both ends of the negative electrode plate, the thickness ratio value H1 / H2 of the protrusions is 6%, and the width ratio value H3 / H4 is 15%. The surface of the positive electrode plate is flat, the thickness is uniform, and no protrusion is formed at the end of the positive electrode plate, that is, the value H1 / H2 of the thickness ratio of the end of the positive electrode plate is 0, The width ratio value H3 / H4 is zero. Other than that, the electrode plate group and the lead storage battery were produced under the same installation conditions as in Example F.
 表1に示すように,実施例Fと比較して、実施例Xにおける電池のサイクル寿命特性は若干低下している。これは、繰り返し充放電中に、負極板格子の変形及び成長能力が正極板の格子より低いためである。 As shown in Table 1, as compared with Example F, the cycle life characteristics of the battery in Example X are slightly deteriorated. This is because the negative electrode plate lattice has a lower deformation and growth capability than the positive plate lattice during repeated charge and discharge.
 (実施例Y)
 実施例Yにおいて、正極板及び負極板それぞれの両端部に突起が形成され、上記突起の厚さの比の値H1/H2は6%であり、幅の比の値H3/H4は15%である。それ以外、その他は実施例Fと同様の設置条件で極板群及び鉛蓄電池を作製した。
(Example Y)
In Example Y, protrusions are formed at both ends of each of the positive electrode plate and the negative electrode plate, the thickness ratio value H1 / H2 of the protrusions is 6%, and the width ratio value H3 / H4 is 15%. is there. Other than that, the electrode plate group and the lead storage battery were produced under the same installation conditions as in Example F.
 表1に示すように,実施例Fと比較して、実施例Yにおける電池の充放電特性(放電効率、放電容量及びハイレート放電容量)は若干低下している。これは、正極板及び負極板それぞれの両端部に突起が形成され、正極板と負極板との間隔が大きすぎて、抵抗が大きくなるためである。 As shown in Table 1, compared with Example F, the charge / discharge characteristics (discharge efficiency, discharge capacity, and high rate discharge capacity) of the battery in Example Y are slightly lowered. This is because protrusions are formed at both ends of each of the positive electrode plate and the negative electrode plate, the distance between the positive electrode plate and the negative electrode plate is too large, and the resistance increases.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 本発明は、サイクル寿命、充放電効率、放電容量及びハイレート放電容量がともに優れた鉛蓄電池を提供し、該鉛蓄電池は車両を起動する電源、照明電源及び予備電源として用いられるのではなく、主電源用途、即ち、独立した充放電設備用電源としても広く用いられている。例えば、電動自動車、電動フォークリフト、電動バス、電動自転車、電動バイク、電動スクータ、小型電動モペッド、ゴルフ用車、電気機関車等の動力電源、ソーラー用電池等の電気エネルギー蓄積装置である。 The present invention provides a lead storage battery having excellent cycle life, charge / discharge efficiency, discharge capacity, and high-rate discharge capacity, and the lead storage battery is not used as a power source for starting a vehicle, an illumination power source, and a standby power source. It is also widely used as a power source, that is, an independent power source for charging and discharging equipment. For example, electric power storage devices such as electric vehicles, electric forklifts, electric buses, electric bicycles, electric motorcycles, electric scooters, small electric mopeds, golf cars, electric locomotives, and solar batteries.

Claims (12)

  1.  極板群、電解液及びセル電池チャンバーを有する複数のセル電池を有し、前記極板群及び前記電解液は前記セル電池チャンバーに収容され、前記極板群は複数の正極板及び複数の負極板がセパレータを介して交互に配列したものであり、前記正極板は、正極極耳を有する正極集電体と該正極集電体によって保持された正極活物質層とを備え、前記負極板は、負極極耳を有する負極集電体と該負極集電体によって保持された負極活物質層とを備える鉛蓄電池において、
     前記セパレータはAGMセパレータであり、前記極板群及び前記電解液が前記セル電池チャンバーに収容され状態での前記セパレータの密度は117~129g/dmという範囲にあり、前記正極板及び前記負極板のうちの少なくとも1つの極板の集電体はエキスバンド法で作製したエキスバンド格子であり、前記極板は突起を有する突起状両端部と該両端部の間の平坦中間部分とを含み、前記両端部の厚さが前記中間部分の厚さよりも大きく、前記中間部分の厚さをH2とし、前記両端部の厚さと前記中間部分の厚さとの差をH1とした時に、H1とH2の比の値H1/H2は3%~9%であることを特徴とする鉛蓄電池。
    A plurality of cell batteries having an electrode plate group, an electrolytic solution, and a cell battery chamber, wherein the electrode plate group and the electrolyte solution are accommodated in the cell battery chamber, and the electrode plate group includes a plurality of positive electrode plates and a plurality of negative electrodes. The plates are alternately arranged via separators, and the positive electrode plate includes a positive electrode current collector having a positive electrode ear and a positive electrode active material layer held by the positive electrode current collector, In a lead storage battery comprising a negative electrode current collector having a negative electrode ear and a negative electrode active material layer held by the negative electrode current collector,
    The separator is an AGM separator, and the density of the separator in a state where the electrode plate group and the electrolytic solution are accommodated in the cell battery chamber is in a range of 117 to 129 g / dm 3 , and the positive electrode plate and the negative electrode plate The current collector of at least one of the electrode plates is an extended grating produced by an extended band method, and the electrode plate includes protruding end portions having protrusions and flat intermediate portions between the both end portions, When the thickness of the both end portions 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 both end portions and the thickness of the intermediate portion is H1, H1 and H2 Lead acid battery characterized in that the ratio value H1 / H2 is between 3% and 9%.
  2.  請求項1に記載の鉛蓄電池において、前記比の値H1/H2は4%~8%であることを特徴とする鉛蓄電池。 2. The lead acid battery according to claim 1, wherein the ratio value H1 / H2 is 4% to 8%.
  3.  請求項1に記載の鉛蓄電池において、前記端部の幅は前記極板の全幅の5%~25%であることを特徴とする鉛蓄電池。 2. The lead acid battery according to claim 1, wherein the width of the end portion is 5% to 25% of the entire width of the electrode plate.
  4.  請求項3に記載の鉛蓄電池において、前記端部の幅は前記極板の全幅の10%~20%であることを特徴とする鉛蓄電池。 4. The lead acid battery according to claim 3, wherein the width of the end portion is 10% to 20% of the entire width of the electrode plate.
  5.  請求項1に記載の鉛蓄電池において、前記突起状両端部のそれぞれが有する突起は、前記極板の同一側に形成されていることを特徴とする鉛蓄電池。 2. The lead acid battery according to claim 1, wherein the protrusions of each of the projecting end portions are formed on the same side of the electrode plate.
  6.  請求項1に記載の鉛蓄電池において、前記突起状両端部のそれぞれが有する突起は、前記極板の異なる側に形成されていることを特徴とする鉛蓄電池。 2. The lead acid battery according to claim 1, wherein the protrusions of each of the projecting end portions are formed on different sides of the electrode plate.
  7.  請求項1~6の何れか1つに記載の鉛蓄電池において、前記極板の活物質層の密度である鉛ペースト密度は4.15g/cm~5.0g/cmであることを特徴とする鉛蓄電池。 In lead-acid battery according to any one of claims 1 to 6, characterized in that lead paste density is the density of the active material layer of the electrode plate is 4.15g / cm 3 ~ 5.0g / cm 3 Lead storage battery.
  8.  請求項1~6の何れか1つに記載の鉛蓄電池において、前記極板は正極板であることを特徴とする鉛蓄電池。 The lead acid battery according to any one of claims 1 to 6, wherein the electrode plate is a positive electrode plate.
  9.  請求項1に記載の鉛蓄電池において、前記正極板の活物質層の密度である鉛ペースト密度は4.15g/cm~4.45g/cmであることを特徴とする鉛蓄電池。 In lead-acid battery according to claim 1, lead-acid battery, wherein the lead paste density is the density of the active material layer of the positive electrode plate is 4.15g / cm 3 ~ 4.45g / cm 3.
  10.  請求項1~6の何れか1つに記載の鉛蓄電池において、前記鉛蓄電池の化成後の前記電解液の密度は1.33~1.35g/cmであることを特徴とする鉛蓄電池。 7. The lead acid battery according to claim 1, wherein the density of the electrolytic solution after the formation of the lead acid battery is 1.33 to 1.35 g / cm 3 .
  11.  請求項1に記載の鉛蓄電池において、前記電解液は硫酸と水とを含む硫酸水溶液であることを特徴とする鉛蓄電池。 2. The lead acid battery according to claim 1, wherein the electrolyte is an aqueous sulfuric acid solution containing sulfuric acid and water.
  12.  請求項1又は11に記載の鉛蓄電池において、前記電解液には、該電解液に完全に溶解可能な少量の添加剤が含まれていることを特徴とする鉛蓄電池。 12. The lead acid battery according to claim 1 or 11, wherein the electrolyte contains a small amount of an additive that can be completely dissolved in the electrolyte.
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