WO2018105134A1 - Batterie d'accumulateurs au plomb liquide, procédé de charge/décharge de la batterie d'accumulateurs au plomb liquide, et système d'alimentation électrique - Google Patents

Batterie d'accumulateurs au plomb liquide, procédé de charge/décharge de la batterie d'accumulateurs au plomb liquide, et système d'alimentation électrique Download PDF

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WO2018105134A1
WO2018105134A1 PCT/JP2017/005721 JP2017005721W WO2018105134A1 WO 2018105134 A1 WO2018105134 A1 WO 2018105134A1 JP 2017005721 W JP2017005721 W JP 2017005721W WO 2018105134 A1 WO2018105134 A1 WO 2018105134A1
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Prior art keywords
electrode plate
acid battery
separator
liquid lead
negative electrode
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PCT/JP2017/005721
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English (en)
Japanese (ja)
Inventor
素子 原田
真吾 荒城
岩崎　富生
隆之 木村
大越　哲郎
本田　光利
博史 春名
大郊 高松
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日立化成株式会社
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Priority to JP2018554803A priority Critical patent/JP6965892B2/ja
Publication of WO2018105134A1 publication Critical patent/WO2018105134A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a liquid lead acid battery, a method for charging and discharging a liquid lead acid battery, and a power supply system.
  • Lead storage batteries are widely used for industrial purposes, and are used, for example, for automobile batteries, backup power supplies, and main power supplies for electric vehicles.
  • an idling stop-and-start system (hereinafter referred to as “ISS”) that stops the engine during power generation control, waiting for a signal, or the like is employed for the purpose of carbon dioxide emission regulation measures, fuel efficiency reduction, and the like. It has become so.
  • stratification means that sulfate ions (SO 4 2 ⁇ ) and hydrogen sulfate ions (HSO 4 ⁇ ) (hereinafter collectively referred to as “sulfate ions”) in the electrolyte solution are precipitated by repeated charge and discharge.
  • SO 4 2 ⁇ sulfate ions
  • HSO 4 ⁇ hydrogen sulfate ions
  • Patent Document 1 discloses a liquid lead that ensures liquid retention by extending a porous resin layer containing butyl rubber or the like on the surface of the electrode and can extend the life of a lead storage battery. A storage battery is described.
  • the lead-acid battery as described in Patent Document 1 still has room for improvement in terms of suppressing the stratification of the electrolyte, particularly when used under conditions where the remaining capacity is small.
  • an object of the present invention is to suppress the stratification of the electrolyte and improve the life in a liquid lead acid battery used with a predetermined remaining capacity.
  • a liquid body lead-acid battery used with a predetermined remaining capacity has a membrane body having pores having an average pore diameter of 15 ⁇ m or less between the negative electrode and the separator. It has been found that when it is provided, the stratification of the electrolytic solution can be suppressed and the durability can be improved.
  • the present invention provides a positive electrode plate, a negative electrode plate, a separator disposed between the positive electrode plate and the negative electrode plate, a film body disposed between the negative electrode plate and the separator, and an electrolytic solution. And a positive electrode plate, a negative electrode plate, a separator, a film body, and a battery case containing an electrolyte solution.
  • the film body has pores having an average pore diameter of 15 ⁇ m or less, and the ratio of the remaining capacity to the full charge capacity Is a liquid lead-acid battery that is used to be 90% or less.
  • the film body includes a nonwoven fabric containing inorganic fibers or a nonwoven fabric containing organic fibers and inorganic fibers.
  • the separator is a bag-shaped separator, and the negative electrode plate and the film body are accommodated in the separator.
  • the membrane body has a thickness of 0.3 mm or less, a porosity of 20% or more, and a basis weight of 30 g / m 2 to 50 g / m 2 .
  • the present invention is a method for charging and discharging a liquid lead storage battery, wherein the liquid lead storage battery is charged and discharged so that a ratio of a remaining capacity to a full charge capacity is 90% or less.
  • the present invention includes the liquid lead-acid battery described above and a control unit that controls charging / discharging of the liquid lead-acid battery, and the control unit has a remaining capacity with respect to a full charge capacity of the liquid lead-acid battery. It is a power supply system which controls charging / discharging so that the ratio may become 90% or less.
  • FIG. 3 is a schematic cross-sectional view showing a cross section taken along the line II in FIG. 2. It is a figure which shows the component of the alternator regeneration vehicle which concerns on one Embodiment.
  • FIG. 1 is a perspective view showing the overall configuration and internal structure of a liquid lead acid battery (hereinafter also simply referred to as “lead acid battery”) according to an embodiment.
  • the lead storage battery 1 includes a battery case 2 having an upper surface opened and a lid 3 for closing the opening of the battery case 2.
  • the battery case 2 and the lid 3 are made of, for example, polypropylene.
  • the lid 3 is provided with a negative electrode terminal 4, a positive electrode terminal 5, and a liquid port plug 6 that closes a liquid injection port provided in the lid 3.
  • an electrode group 7 Inside the battery case 2 are an electrode group 7, a negative pole 8 connecting the electrode group 7 to the negative terminal 4, a positive pole (not shown) connecting the electrode group 7 to the positive terminal 5, dilute sulfuric acid, etc.
  • the electrolyte solution is accommodated.
  • the lead storage battery 1 may have a width dimension equal to or greater than D in a category defined in JIS D5301.
  • the width dimension of the lead storage battery 1 may be D, E, F, G, or H, for example, as defined in JIS D5301.
  • the lead-acid battery 1 may have a width dimension of LBN0 or more or LN0 or more in the category defined in EN 50342-2.
  • the width dimension of the lead storage battery 1 may be, for example, LBN 0 to 6 or LN 0 to 6 according to the classification defined in EN 50342-2.
  • the lead storage battery 1 may have a width dimension of 170 mm or more in one embodiment.
  • the width dimension of the lead storage battery 1 may be, for example, 175 mm or more or 180 mm or more, or 280 mm or less or 225 mm or less.
  • FIG. 2 is a perspective view showing the electrode group 7.
  • the electrode group 7 includes a plate-like negative electrode plate 9 containing metallic lead (Pb) as an active material, a plate-like positive electrode plate 10 containing lead dioxide (PbO 2 ) as an active material, and a negative electrode A separator 11 disposed between the plate 9 and the positive electrode plate 10 is provided.
  • the electrode group 7 has a structure in which a plurality of negative electrode plates 9 and positive electrode plates 10 are alternately stacked in a direction substantially parallel to the opening surface of the battery case 2 via separators 11. That is, the negative electrode plate 9 and the positive electrode plate 10 are arranged so that their main surfaces extend in a direction perpendicular to the opening surface of the battery case 2.
  • the ear portions 9 a of the plurality of negative electrode plates 9 are collectively welded by the negative side strap 12.
  • the ears 10 a of the plurality of positive electrode plates 10 are collectively welded by the positive side strap 13.
  • the negative side strap 12 and the positive side strap 13 are connected to the negative terminal 4 and the positive terminal 5 through the negative pole 8 and the positive pole, respectively.
  • FIG. 3 is a schematic cross-sectional view showing a cross section taken along the line II in FIG. As shown in FIG. 3, a film body 14 is provided between the negative electrode plate 9 and the separator 11.
  • the separator 11 is formed in a bag shape, for example, and the negative electrode plate 9 and the film body 14 are accommodated in the separator 11.
  • Examples of the material forming the separator 11 include polyethylene (PE) and polypropylene (PP).
  • the separator 11 may be one in which inorganic particles such as SiO 2 and Al 2 O 3 are attached to a woven fabric, a nonwoven fabric, a porous film or the like formed of these materials.
  • the thickness of the separator 11 is preferably 0.1 mm to 0.5 mm, more preferably 0.2 mm to 0.3 mm.
  • the thickness of the separator 11 is 0.1 mm or more, the strength of the separator can be secured.
  • the thickness of the separator 11 is 0.5 mm or less, an increase in the internal resistance of the battery can be suppressed.
  • the average pore diameter of the separator 11 is preferably 10 nm to 500 nm, more preferably 30 nm to 200 nm.
  • the average pore diameter of the separator 11 is 10 nm or more, sulfate ions can be suitably passed, and the diffusion rate of sulfate ions can be ensured.
  • the average pore diameter of the separator 11 is 500 nm or less, the growth of lead dendrite is suppressed, and a short circuit hardly occurs.
  • the film body 14 is provided in close contact with the negative electrode plate 9 so as to cover the surface of the negative electrode plate 9.
  • the film body 14 may be, for example, a sheet shape or a bag shape.
  • the film body 14 covers the surface of the negative electrode plate 9 so as to be wound around the negative electrode plate 9.
  • the negative electrode plate 9 is accommodated in the film body 14.
  • the film body 14 includes, for example, a nonwoven fabric, and preferably includes a nonwoven fabric containing inorganic fibers.
  • the nonwoven fabric containing inorganic fibers may be an inorganic nonwoven fabric containing only inorganic fibers as fibers, or an organic / inorganic mixed nonwoven fabric containing organic fibers and inorganic fibers as fibers.
  • inorganic fibers include SiO 2 fibers (glass fibers).
  • the organic fiber include synthetic fibers such as polyethylene, polypropylene, polyester, nylon, and aramid.
  • the organic / inorganic mixed nonwoven fabric may further contain inorganic powder formed of SiO 2 or the like.
  • the average pore diameter is 15 ⁇ m or less from the viewpoint of suppressing the stratification of the electrolytic solution.
  • the average pore diameter of the film body 14 is preferably 14 ⁇ m or less, 13 ⁇ m or less, 12 ⁇ m or less, 11 ⁇ m or less, or 10 ⁇ m or less from the viewpoint of further suppressing the stratification of the electrolytic solution.
  • the average pore diameter of the film body 14 is preferably 0.1 ⁇ m or more, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m from the viewpoint of improving the output of the battery.
  • the average pore diameter of the membrane body is an X corresponding to an intermediate value between the minimum value and the maximum value on the Y axis (pore volume or pore specific surface area) of the distribution curve in the cumulative pore diameter distribution measured by the mercury intrusion method. It is calculated as the median diameter which is the value of the axis (pore diameter).
  • the average pore diameter of the membrane can be measured by, for example, Shimadzu Corporation Autopore IV 9500.
  • the present inventors consider the reason why the stratification of the electrolytic solution is suppressed by providing the film body 14 as follows. That is, the aggregate of sulfate ions generated by the charging reaction collides with the pores of the film body 14 and gradually settles in the electrolytic solution as high-concentration particles while diffusing. When the film body 14 having a specific average pore diameter is provided, the sedimentation rate of sulfate ions is reduced as compared with the case where the film body 14 is not provided, so that stratification can be suppressed. When the remaining capacity of the lead storage battery 1 is small, the amount of sulfate ions is particularly large, and this tendency is noticeable.
  • the fiber diameter of the fibers constituting the nonwoven fabric is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the specific surface area of the membrane body 14 is increased and the space for holding sulfate ions can be increased. Therefore, the ability of the membrane body 14 to retain sulfate ions can be further improved. it can.
  • the fiber diameter is preferably 1 ⁇ m or more from the viewpoint of suppressing fiber breakage, tearing of the film body, etc., and ensuring durability.
  • the thickness of the film body 14 is preferably 0.3 mm or less, more preferably 0.25 mm or less, still more preferably 0.2 mm or less, and particularly preferably 0.15 mm or less from the viewpoint of suppressing an increase in internal resistance. .
  • the thickness of the film body 14 is, for example, 0.03 mm or more from the viewpoint of the ability to prevent the precipitation of sulfate ions, the influence on the battery reaction, the strength, and the like.
  • the thickness of the film body 14 is determined according to the thickness of the fibers constituting the nonwoven fabric.
  • the porosity of the film body 14 is preferably 20% or more, more preferably 40% or more, and still more preferably 60% or more, from the viewpoint of ensuring the diffusibility of sulfate ions and increasing the space for holding sulfate ions. Especially preferably, it is 80% or more.
  • the porosity of the film body 14 may be 95% or less, for example.
  • the porosity of the film body is calculated from the actual volume and the apparent volume according to the following formulas (1) to (3) for a sample cut from the film body into a rectangular parallelepiped having an appropriate size.
  • Porosity (%) ⁇ 1 ⁇ (actual volume / apparent volume) ⁇ ⁇ 100 (1)
  • Actual volume (cm 3 ) actual value of weight (g) / density (g / cm 3 ) (2)
  • Apparent volume (cm 3 ) length (cm) ⁇ width (cm) ⁇ thickness (cm) (3) Note that measured values are used for the length, width, and thickness of the sample when calculating the apparent volume.
  • the basis weight of the film body 14 is preferably 30 g / m 2 to 50 g / m 2 , more preferably 35 g / m 2 to 50 g / m 2 , and still more preferably from the viewpoint of coexistence of suppression of stratification and suppression of increase in internal resistance. Is 40 g / m 2 to 50 g / m 2 .
  • the basis weight is calculated as a mass per unit area of the film body 14.
  • the film body 14 is provided so as to cover all of the main surface (the surface facing the separator 11), the side surface, and the bottom surface of the negative electrode plate 9, and to be in contact with (in close contact with) the surfaces.
  • the film body may be provided between the negative electrode plate 9 and the separator 11 so as to be separated from the negative electrode plate 9.
  • the film body 14 may be provided on the surface of the separator 11 on the negative electrode side, for example.
  • the film body 14 is preferably provided so as to be in contact with (in close contact with) the surface of the negative electrode plate 9.
  • the film body 14 covers all of the main surface (the surface facing the separator 11), the side surface, and the bottom surface of the negative electrode plate 9. In other embodiments, the film body is the main surface of the negative electrode plate 9. It may be provided so as to cover only the surface (the surface facing the separator 11).
  • the lead storage battery described above is used so that the ratio of the remaining capacity to the full charge capacity (remaining capacity / full charge capacity) is 90% or less.
  • the ratio (remaining capacity / full charge capacity) may be 85% or less or 80% or less, or 50% or more, 55% or more, or 60% or more. Note that the lead storage battery need not be used so that the ratio of the remaining capacity to the full charge capacity steadily falls within the above range, but at least temporarily (that is, the minimum value of the ratio of the remaining capacity to the full charge capacity). May be used so as to be within the above range.
  • the power supply system is mounted in an engine room of an alternator regenerative vehicle ( ⁇ HEV).
  • ⁇ HEV alternator regenerative vehicle
  • the present invention is not limited to this embodiment.
  • ⁇ HEV refers to a gasoline vehicle or a diesel vehicle that has an ISS function, can receive regenerative power supplied from an alternator, and includes an electricity storage device that can discharge to a discharge load.
  • FIG. 4 is a diagram showing components of an alternator regenerative vehicle according to an embodiment.
  • the alternator regenerative vehicle 21 includes a vehicle control unit (ECU) 22, an alternator 23, a discharge load 24, and a power supply system 25.
  • ECU vehicle control unit
  • the vehicle control unit 22 controls the operation of the alternator regenerative vehicle 21 as a whole.
  • the vehicle control unit 22 grasps whether the ignition switch is in the OFF position, the ON / ACC position, or the START position, and determines the vehicle state such as the operating state of the accelerator, the brake, the engine, the speed, and the acceleration. Grasping and running control according to the grasped state.
  • the vehicle control unit 22 can communicate with a control unit (details will be described later) of the power supply system 25, receives information related to the state of the lead storage battery constituting the power supply system 25, and Vehicle state information (ignition switch position information, alternator operation information, etc.) is transmitted.
  • the alternator 23 is controlled by the vehicle control unit 22 and converts the rotational force of the engine into (regenerative) electric power when the alternator regenerative vehicle 21 is braked or when the accelerator is off.
  • the alternator 23 includes a power generation unit composed of a stator and a rotor, a rectification unit that converts AC power generated by the power generation unit into DC power, and a voltage for making the voltage of the DC power converted by the rectification unit constant. And a regulator.
  • the output voltage of the alternator 23 is set to 14 V, for example.
  • the discharge load 24 includes a starter (cell motor) and auxiliary equipment.
  • auxiliary machines include lamps (lights), engine pumps (spark plugs), air conditioners, fans, radios, televisions, CD players, car navigation systems, and the like.
  • the auxiliary machine is supplied with a minimum voltage (for example, 8V) for operation from the power supply system 25 (lead storage battery 1).
  • the ignition switch is set to the START position, power is supplied from the power supply system 25 (lead storage battery 1) to the starter, the starter rotates, and the starter is connected to the rotation shaft of the engine via the clutch mechanism. The rotational driving force is transmitted and the engine is started.
  • the power supply system 25 includes the lead storage battery 1, the selector 26, the battery controller 27, the current sensor 28, and the control unit 29 described above, and constitutes a 14V power supply system, for example.
  • the lead storage battery 1 can accept the regenerative power supplied from the alternator 23 and can be discharged to the discharge load 24.
  • the selector 26 supplies the regenerative power from the alternator 23 to the lead storage battery 1 and discharges the power from the lead storage battery 1 to the discharge load 24.
  • the power supply system 25 further includes a second storage battery (not shown) other than the lead storage battery 1, the selector 26 receives the regenerative power supplied from the alternator 23 from the alternator 23 to the lead storage battery. It plays the role of a switch connected to one of the first and second storage batteries, and is connected to the discharge load 24 from either the lead storage battery 1 or the second storage battery when discharging from the electricity storage device to the discharge load 24. To act as a switch.
  • the battery controller 27 detects the battery state such as the temperature, voltage, current, etc. of the lead storage battery 1 during charge / discharge (during vehicle travel and before vehicle travel). Specifically, a temperature sensor attached to the lead storage battery 1 is connected to the battery controller 27, and the battery controller 27 samples the voltage of the temperature sensor every predetermined time (for example, 10 ms) and stores the sampling result in the RAM. Store. The battery controller 27 is connected to the positive terminal and the negative terminal of the lead storage battery 1 and detects the voltage of the lead storage battery 1.
  • a current sensor 28 such as a Hall element or a shunt resistor is disposed between the selector 26 and the positive electrode terminal of the lead storage battery 1, and the battery controller 27 supplies a current flowing through the lead storage battery 1 through the current sensor 28 for a predetermined time ( Sampling is performed every 2 ms), and the sampling result is stored in the RAM. Moreover, the battery controller 27 detects the open circuit voltage and temperature of the lead storage battery 1 at the time of charging / discharging suspension (at the time of vehicle parking).
  • the battery controller 27 is connected to the control unit 29 and transmits information on the temperature, voltage and current of the lead storage battery 1 stored in the RAM to the control unit 29 at the time of charging / discharging. Information regarding the open circuit voltage and temperature is transmitted to the control unit 29.
  • the control unit 29 is configured as a microprocessor including a microcontroller, a communication IC, an I / O, an input port, an output port, and the like.
  • FIG. Represents.
  • the microcontroller for example, a CPU that grasps (calculates) the battery state of the lead-acid battery 1, a ROM that stores program data such as a basic control program and a table, works as a work area for the CPU, and temporarily stores various data. It is composed of a RAM and an internal bus connecting them. The internal bus is connected to the external bus, and the external bus is connected to the battery controller 27 via the input port. An output port for outputting a signal to the selector 26, an I / O, and a communication IC for communicating with the vehicle control unit 22 are connected to the external bus.
  • the microcontroller and input port of the control unit 29 are in the state grasping unit 30 in FIG. 4, the microcontroller and output port are in the selector control unit in FIG. 4, and the communication IC and I / O are in the communication unit 6C in FIG. Correspond.
  • the state grasping unit 30 temporarily stores the detection data transmitted from the battery controller 27 in the RAM of the microcontroller, and calculates (estimates) the battery state and the like of the lead storage battery 1.
  • the selector control unit 31 controls the selector 26 according to the operation information of the alternator 23 received from the vehicle control unit 22 and the battery state of the lead storage battery 1 calculated by the state grasping unit 30.
  • the communication unit 32 transmits the battery state of the lead storage battery 1 calculated by the state grasping unit 30 to the vehicle control unit 22 every predetermined time (for example, 2 ms), and from the vehicle control unit 22 to the vehicle state information (position of the ignition switch). Information, operation information of the alternator 23).
  • the control unit 29 controls charging / discharging of the lead storage battery 1 such that the ratio of the remaining capacity to the full charge capacity of the lead storage battery 1 (remaining capacity / full charge capacity) is 90% or less.
  • the control unit 29 may control charging / discharging of the lead storage battery 1 so that the ratio (remaining capacity / full charge capacity) is 85% or less or 80% or less, and is 50% or more, 55% or more, or 60 You may control charging / discharging of the lead storage battery 1 so that it may become more than%. Note that the control unit 29 does not need to control the ratio of the remaining capacity with respect to the full charge capacity of the lead storage battery 1 to be constantly within the above range, but at least temporarily (that is, the remaining capacity with respect to the full charge capacity).
  • one Embodiment of this invention is the charging / discharging method of the lead storage battery 1 which charges / discharges the lead storage battery 1 so that the ratio of the remaining capacity with respect to a full charge capacity may become in said range.
  • Example 1 A paste type electrode plate in which a lead alloy lattice filled with a paste prepared by kneading lead powder mainly composed of lead monoxide with dilute sulfuric acid was used. Thereafter, an unformed electrode plate was obtained through aging and drying steps.
  • the unformed positive electrode plate and negative electrode plate are both composed of a mixture of divalent lead compounds such as lead monoxide (PbO) and tribasic dilute lead sulfate (3PbO ⁇ PbSO 4 ⁇ H 2 O). ing.
  • PbO lead monoxide
  • 3PbO ⁇ PbSO 4 ⁇ H 2 O tribasic dilute lead sulfate
  • the unformed material of the positive electrode plate is oxidized to lead dioxide (PbO 2 ), and the unformed material of the negative electrode plate is reduced to spongy lead (Pb) to obtain an already formed electrode plate (positive electrode plate, negative electrode plate). It was.
  • An inorganic non-woven fabric (main component: SiO 2 ) as shown in Table 1 was used as the film body and placed on the negative electrode plate.
  • the separator a bag-like polyethylene separator having a thickness of 0.25 mm and an average pore diameter of 30 nm to 200 nm was used, and the negative electrode plate and the film body were accommodated in the separator.
  • D size using dilute sulfuric acid as electrolyte JIS D5301, width: 173 mm, box height: 204 mm, negative plate width: 145 mm, negative plate height (including upper frame)) : 113 mm.
  • a lead storage battery with a rated capacity of 60 Ah was produced.
  • the average pore diameter of the membrane was measured with Autopore IV 9500 manufactured by Shimadzu Corporation.
  • the average pore diameter of the membrane body is an X corresponding to an intermediate value between the minimum value and the maximum value on the Y axis (pore volume or pore specific surface area) of the distribution curve in the cumulative pore diameter distribution measured by the mercury intrusion method.
  • the median diameter was calculated as the value of the axis (pore diameter).
  • the internal resistance of the lead-acid battery that had been initially charged in advance was evaluated using a 1 kHz AC m ⁇ meter.
  • the specific evaluation criteria are indicated by the value of the internal resistance when the internal resistance of the lead storage battery when the film body is not provided (Comparative Example 1) is 100.
  • the value of the internal resistance is preferably less than 125, more preferably less than 120, and even more preferably less than 110.
  • the results are shown in Table 1.
  • Example 1 the life performance of the lead storage battery when used so that the ratio of the remaining capacity to the full charge capacity was 50% was measured as follows. First, a fully charged lead storage battery that had been fully charged was placed in a water bath set to a temperature of 40 ⁇ 2 ° C. Next, the following cycle units (a) and (b) were repeated in order. In a 60 Ah lead-acid battery, the 20 hour rate current is 3 A. In addition, this test was a cycle test simulating the use of a lead storage battery in an ISS car, and it was determined that the life was reached when the voltage of the lead storage battery fell below 10.0V. The results are shown in Table 1. (A) Discharge for 2 hours at 15 A (corresponding to 5 times the 20 hour current). (B) Charging for 5 hours up to 15A (equivalent to 5 times the 20-hour current). The charging upper limit voltage at that time was 15.6 ⁇ 0.1V.
  • the vertical specific gravity difference was calculated as 100, and the vertical specific gravity difference was calculated.
  • the difference in specific gravity between the upper and lower sides is preferably less than 70, more preferably less than 50. When the difference in specific gravity between the upper and lower sides was less than 70, it was judged that stratification was suppressed.
  • Examples 2 to 5 A lead-acid battery was produced and evaluated in the same manner as in Example 1 except that the ratio of the remaining capacity to the full charge capacity was changed as shown in Table 1 in the life test and the evaluation of the stratification suppressing effect.
  • Examples 6 and 7 A lead-acid battery was produced and evaluated in the same manner as in Example 1 except that the inorganic nonwoven fabric as shown in Table 1 was used as the film body.
  • Example 3 and 4 were used except that an organic / inorganic mixed non-woven fabric (perforated sheet. Non-woven fabric composed of mixed fiber containing pulp, glass fiber and silica powder) was used instead of the inorganic non-woven fabric.
  • the lead storage battery was manufactured and evaluated.
  • Example 10 The size of the lead storage battery is LN1 size (EN 50342-2. Width: 175 mm, Box height: 190 mm. Negative electrode plate width: 143 mm, Negative electrode plate height (including upper frame): 100 mm) A lead-acid battery was produced and evaluated in the same manner as in Example 4 except that the change was made.
  • ⁇ Comparative example 2> A lead-acid battery was produced and evaluated in the same manner as in Example 1 except that the film body was not provided on the negative electrode plate and that the positive electrode plate was accommodated in the separator instead of the negative electrode plate.
  • Example 3 A lead-acid battery was produced in the same manner as in Example 1 except that the film body was provided on the positive electrode plate without providing the film body on the negative electrode plate, and the positive electrode plate and the film body were accommodated in the separator instead of the negative electrode plate. And evaluated.
  • Example 4 A lead-acid battery was prepared and evaluated in the same manner as in Example 4 except that the inorganic nonwoven fabric as shown in Table 1 was used as the film body.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

Le but de la présente invention est de réduire au minimum la stratification d'une solution électrolytique et d'améliorer la durée de vie dans une batterie d'accumulateurs au plomb liquide utilisée à une capacité restante prédéterminée. Un mode de réalisation de la présente invention est une batterie d'accumulateurs au plomb liquide comprenant : une plaque d'électrode positive; une plaque d'électrode négative; un séparateur disposé entre la plaque d'électrode positive et la plaque d'électrode négative; une membrane disposée entre la plaque d'électrode négative et le séparateur; une solution électrolytique; et un boîtier de batterie pour recevoir la plaque d'électrode positive, la plaque d'électrode négative, le séparateur, la membrane et la solution électrolytique, la membrane comprenant des pores ayant une taille de pore moyenne de 15 µm ou moins et ladite batterie d'accumulateurs au plomb liquide étant utilisée de telle sorte que le rapport de la capacité restante à la capacité de pleine charge est de 90 % ou moins.
PCT/JP2017/005721 2016-12-07 2017-02-16 Batterie d'accumulateurs au plomb liquide, procédé de charge/décharge de la batterie d'accumulateurs au plomb liquide, et système d'alimentation électrique WO2018105134A1 (fr)

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PCT/JP2016/086395 WO2018105060A1 (fr) 2016-12-07 2016-12-07 Batterie au plomb-acide liquide

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020009630A (ja) * 2018-07-09 2020-01-16 日立化成株式会社 鉛蓄電池

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Publication number Priority date Publication date Assignee Title
JP2003077445A (ja) * 2001-08-31 2003-03-14 Yuasa Corp 鉛蓄電池
WO2012157311A1 (fr) * 2011-05-13 2012-11-22 新神戸電機株式会社 Accumulateur au plomb
JP2013541162A (ja) * 2010-09-22 2013-11-07 ダラミック エルエルシー 改良された鉛蓄電池セパレータ、電池及び関連の方法
JP2016177872A (ja) * 2015-03-18 2016-10-06 日立化成株式会社 鉛蓄電池
WO2017033497A1 (fr) * 2015-08-24 2017-03-02 日立化成株式会社 Séparateur d'accumulateur au plomb, accumulateur au plomb et procédé de fabrication correspondant

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Publication number Priority date Publication date Assignee Title
JP2921332B2 (ja) * 1993-05-24 1999-07-19 新神戸電機株式会社 鉛蓄電池用ガラスマット
JP2005108538A (ja) * 2003-09-29 2005-04-21 Nippon Sheet Glass Co Ltd 密閉型鉛蓄電池用セパレータおよび密閉型鉛蓄電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003077445A (ja) * 2001-08-31 2003-03-14 Yuasa Corp 鉛蓄電池
JP2013541162A (ja) * 2010-09-22 2013-11-07 ダラミック エルエルシー 改良された鉛蓄電池セパレータ、電池及び関連の方法
WO2012157311A1 (fr) * 2011-05-13 2012-11-22 新神戸電機株式会社 Accumulateur au plomb
JP2016177872A (ja) * 2015-03-18 2016-10-06 日立化成株式会社 鉛蓄電池
WO2017033497A1 (fr) * 2015-08-24 2017-03-02 日立化成株式会社 Séparateur d'accumulateur au plomb, accumulateur au plomb et procédé de fabrication correspondant

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020009630A (ja) * 2018-07-09 2020-01-16 日立化成株式会社 鉛蓄電池
JP7274830B2 (ja) 2018-07-09 2023-05-17 エナジーウィズ株式会社 鉛蓄電池

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JPWO2018105060A1 (ja) 2019-10-24
JP6908052B2 (ja) 2021-07-21
WO2018105060A1 (fr) 2018-06-14
JPWO2018105134A1 (ja) 2019-10-24

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