WO2013046499A1 - エネルギー貯蔵用鉛蓄電池 - Google Patents

エネルギー貯蔵用鉛蓄電池 Download PDF

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WO2013046499A1
WO2013046499A1 PCT/JP2012/003697 JP2012003697W WO2013046499A1 WO 2013046499 A1 WO2013046499 A1 WO 2013046499A1 JP 2012003697 W JP2012003697 W JP 2012003697W WO 2013046499 A1 WO2013046499 A1 WO 2013046499A1
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active material
positive electrode
negative electrode
electrode active
battery
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PCT/JP2012/003697
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English (en)
French (fr)
Japanese (ja)
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静 張
和成 安藤
佐々木　健浩
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パナソニック株式会社
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Priority to JP2012542717A priority Critical patent/JP5190562B1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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 lead storage battery for energy storage. More specifically, the present invention relates to an energy storage lead-acid battery having excellent discharge capacity and charge acceptance at low temperatures.
  • Valve-controlled lead-acid batteries have advantages such as low cost, stable output, and maintenance-free, and have been widely used in fields such as vehicle start-up, standby power supply, and energy storage system.
  • Lead storage batteries used in energy storage systems (simply called “lead storage batteries for energy storage”) convert renewable energy in the natural world, such as solar energy and wind energy, into direct current electricity, and then adjust the power to external devices. Can be output.
  • Lead storage batteries for energy storage need to operate in a natural environment for a long period of time, so they need to have good cycle life characteristics as well as excellent discharge capacity and charge acceptance at low temperatures. It is required that In addition, since lead storage batteries for energy storage usually operate at a low discharge rate, it is necessary to achieve desired battery performance under conditions of a low discharge rate by appropriately designing an electrode plate.
  • the conductivity of lead dioxide (PbO 2 ) as a positive electrode active material is relatively inferior, so that there is a problem that discharge at low temperatures is difficult.
  • the positive electrode active material becomes a porous body after chemical conversion, and its pore structure also has a great influence on the discharge characteristics of the lead-acid battery.
  • the main cause of this is that lead sulfate, which is poorly soluble in the positive electrode active material during the discharge process. This is because the generation of crystals closes the pores for supplying the electrolytic solution, making it difficult for the discharge reaction to continue.
  • Patent Document 1 discloses that the total pore volume of the positive electrode active material falls within the range of 0.14 to 0.18 cc / g, thereby improving the discharge capacity of the lead-acid battery during high-rate discharge. ing. Further, in order to achieve a higher capacity of the battery, Patent Document 2 proposes a method in which the volume of pores having a pore diameter of 1 ⁇ m or more in the positive electrode is set to 50% or more of the total pore volume.
  • both of these documents are inventions related to increasing the capacity of lead-acid batteries under normal temperature and high-rate discharge conditions, and the discharge characteristics of lead-acid batteries under low-temperature and low-rate discharge conditions have not been studied.
  • Patent Document 3 describes that 2 to 5% by mass of barium sulfate (BaSO 4 ) is added to the negative electrode active material with respect to the lead powder. And it is described that barium sulfate makes it easy to make the discharge product, that is, lead sulfate, fine as a nucleating agent, thereby improving the charge acceptability of the battery at a low temperature.
  • barium sulfate makes it easy to make the discharge product, that is, lead sulfate, fine as a nucleating agent, thereby improving the charge acceptability of the battery at a low temperature.
  • an object of the present invention is to provide a lead storage battery for energy storage having excellent discharge capacity and charge acceptability at low temperatures.
  • the inventors of the present application have found that the increase in the total pore volume of the positive electrode active material or the increase in the BaSO 4 content in the negative electrode active material does not increase the It was discovered that the discharge capacity cannot be improved. Furthermore, the total pore volume of the positive electrode active material is appropriately reduced and within an appropriate range, and by adding a specific additive to the negative electrode active material, not only has good cycle life characteristics, It was discovered that an energy storage lead-acid battery having excellent discharge capacity and charge acceptance at low temperatures could be provided, and the present invention was completed.
  • the charge / discharge characteristics of the positive electrode can be improved by keeping the total pore volume of the positive electrode active material within an appropriate range.
  • the charge / discharge characteristics of the negative electrode are improved, and the charge / discharge characteristics between the positive and negative electrodes are balanced, thereby charging and discharging characteristics of the entire battery.
  • cycle life characteristics can be improved.
  • a lead storage battery for energy storage includes an electrode plate group and an electrolytic solution impregnated in the electrode plate group, and the electrode plate group includes a plurality of negative electrodes, a plurality of positive electrodes, and a plurality of positive electrodes.
  • the negative electrode includes a negative electrode lattice and a negative electrode active material held in the negative electrode lattice
  • the positive electrode includes a positive electrode lattice and a positive electrode active material held in the positive electrode lattice
  • the separator is an energy storage lead-acid battery separating the positive electrode and the negative electrode
  • the total pore volume of the positive electrode active material is 0.087 to 0.120 cm 3 / g. Is characterized by containing 3.2 to 4.8% by weight of barium sulfate.
  • the positive electrode active material preferably has a large number of pores having a pore diameter of 0.8 ⁇ m.
  • the negative electrode active material preferably contains 0.3 to 2.0% by mass of acetylene black.
  • the negative electrode active material preferably further contains 0.1 to 2.0% by mass of a lignin surfactant.
  • the weight ratio of the negative electrode active material to the positive electrode active material is preferably 0.7 to 0.95.
  • an expanded lattice is used for at least the positive electrode lattice.
  • the separator includes a bag-shaped separator made of synthetic fiber subjected to a hydrophilic treatment and a chip-shaped separator made of glass fiber, the bag-shaped separator contains the positive electrode, and the chip-shaped separator is It is preferable to be sandwiched between a bag-shaped separator and the negative electrode.
  • the synthetic fiber includes at least acrylonitrile fine fibers having a diameter of 0.5 ⁇ m to 2.0 ⁇ m, and further includes acrylonitrile thick fibers having a diameter of 2.5 ⁇ m to 8.0 ⁇ m. More preferably, the content of the acrylonitrile-based fine fibers is greater than the content of the acrylonitrile-based thick fibers.
  • a lead storage battery for energy storage that has not only good cycle life characteristics but also excellent discharge capacity and charge acceptability even at low temperatures.
  • the lead acid battery for energy storage of the present invention is mainly used for a storage system of natural energy such as solar energy.
  • the environment in which these lead acid batteries for energy storage are used is at a low temperature to a normal temperature, For example, it is ⁇ 15 to 40 ° C., and in an extreme case, it can reach ⁇ 30 to 50 ° C. Therefore, the lead acid battery for energy storage of this invention needs to endure long-term use under low temperature. Moreover, the discharge rate which the lead storage battery for energy storage requires is low.
  • low temperature refers to a temperature range of ⁇ 30 ° C. to 0 ° C.
  • low discharge rate refers to a range of 0.01 C to 1.0 C.
  • the positive electrode includes a positive electrode grid having ears and a positive electrode active material held by the positive electrode grid.
  • As the positive electrode grid either an expanded grid or a cast grid often used in lead-acid batteries may be used. From the viewpoint of increasing the capacity of the positive electrode, it is preferable to use an expanded grid for the positive electrode.
  • a known lead powder can be used as the main raw material of the positive electrode active material, and a small amount of other additives such as a conductive material and a binder may be included in addition to the lead powder.
  • the method for producing the positive electrode active material is as follows. That is, after the raw material lead powder (main components are lead and lead monoxide) is kneaded with dilute sulfuric acid, the formed paste is applied to the positive electrode lattice, and after drying, a chemical conversion treatment is performed to obtain a porous body.
  • the chemical conversion treatment may be any one of electrode plate chemical conversion and battery case chemical conversion.
  • the positive electrode active material is formed into a porous body through chemical conversion.
  • the pore structure of the porous body affects the diffusion of the electrolytic solution.
  • the performance of a battery is lowered at a low temperature, and in particular, the discharge performance of the positive electrode is lowered. This is because in a lead-acid battery at a low temperature, the viscosity of sulfuric acid as the electrolyte is increased, and the ion diffusion resistance is increased. Therefore, in order to solve the above problem, it is necessary to improve the pore structure of the positive electrode active material to facilitate the diffusion of the electrolyte and to facilitate the discharge reaction.
  • the pore structure of the positive electrode active material is represented by measuring the pore distribution of the positive electrode active material.
  • the graph of the differential curve of the pore distribution of the positive electrode active material shown in FIG. 3 that is, the differential curve indicating the distribution of the pore volume according to the pore size
  • the graph of the integral curve shown in FIG. 4 is obtained. From the graph of the integral curve, the total pore volume of the positive electrode active material and the specific pore diameter range are obtained. The pore volume can be determined.
  • pore volume here is different from the commonly used “porosity”. Porosity represents only the ratio of the sum of the volumes of all pores in the porous body to the total volume of the porous body, but the pore volume includes the meanings of total pore volume, pore size distribution, average pore size, etc. ing.
  • the “total pore volume of the positive electrode active material” refers to the total volume of all the pores present in the porous body of the positive electrode active material. In this specification, the “total pore volume of the positive electrode active material” Is sometimes simply referred to as “positive electrode pore volume”.
  • the pore structure of the positive electrode active material is controlled by a method such as controlling the particle size of the lead powder of the raw material, changing the concentration or capacity of sulfuric acid, or changing the dropping rate of sulfuric acid. Can be adjusted.
  • the total pore volume of the positive electrode active material tends to decrease as the amount of water or sulfuric acid during the kneading of the positive electrode active material paste is reduced or the density of the paste is increased.
  • the negative electrode includes a negative electrode lattice having ears and a negative electrode active material held by the negative electrode lattice.
  • a negative electrode grid any one of an expanded grid and a cast grid normally used in lead-acid batteries can be used.
  • the negative electrode active material mainly contains metallic lead and lead sulfate, and further contains various additives for improving battery performance or a binder for increasing the adhesion between the respective materials.
  • each additive in the negative electrode active material will be described.
  • the content of each additive is calculated based on the total weight of the negative electrode active material.
  • the nucleating agent examples include barium sulfate (BaSO 4 ) and strontium sulfate (SrSO 4 ).
  • the content of the nucleating agent in the negative electrode active material If the content of the nucleating agent is too large, the amount of the negative electrode active material is relatively decreased, and the structure becomes too dense, so that the charge acceptability at low temperature is deteriorated, and the discharge capacity of the battery is also small. turn into. On the other hand, when the content of the nucleating agent is too small, the role as the nucleating agent cannot be fully exhibited, and the lump of the solidified negative electrode active material becomes large, so that the charge acceptability is also lowered.
  • the nucleating agent is an essential component in the negative electrode active material, and it is preferable to add 3.2 to 4.8% by mass of the nucleating agent with respect to the negative electrode active material.
  • a conductive material may be added to the negative electrode active material.
  • Commonly used conductive materials include acetylene black, carbon black, and graphite.
  • the conductive material is not an essential component in the negative electrode active material, but if a conductive material is added, the conductive performance of the negative electrode can be further improved.
  • the content of the conductive material in the negative electrode active material is preferably 0.3 to 2.0% by mass.
  • the content of the conductive material in the negative electrode active material is preferably 0.3 to 2.0% by mass.
  • a swelling agent further with respect to a negative electrode active material.
  • swelling agents include lignin surfactants (hereinafter simply referred to as lignin) and humic acid.
  • the lignin mainly includes lignin sulfonate having an amphiphilic ionic surfactant structure such as sodium lignin sulfonate and calcium lignin sulfonate.
  • the expansion agent is not an essential component in the negative electrode active material, but by adding the expansion agent to the negative electrode active material, the negative electrode active material can be prevented from contracting and the cycle life of the battery can be further improved. .
  • the expansion agent content in the negative electrode active material can be within the range of the normal content in this field, and is not particularly limited. For example, it can be 0 to 5% by mass. It is preferably 0.0% by mass, more preferably 0.2 to 0.5% by mass.
  • the separator used in the lead storage battery for energy storage of the present invention employs a chip-like separator made of glass fiber, and constitutes an electrode plate group by laminating the chip-like separator between a positive electrode and a negative electrode. It is also possible to adopt a bag-shaped separator made of a synthetic fiber nonwoven fabric subjected to a hydrophilic treatment, and to form a plate group by putting the positive electrode or the negative electrode in the bag-shaped separator and then overlapping the negative electrode or the positive electrode. Good. Moreover, you may use combining said bag-shaped separator and chip-shaped separator.
  • the positive electrode is housed in a bag-shaped separator made of a synthetic fiber nonwoven fabric that has been subjected to a hydrophilic treatment, and the chip-shaped separator made of glass fiber is replaced with a bag-shaped separator and a negative electrode. Is preferably sandwiched between the two.
  • the synthetic fiber is preferably an acrylonitrile fiber, and the synthetic fiber contains at least acrylonitrile fiber having a diameter of 0.5 ⁇ m to 2.0 ⁇ m.
  • the acrylonitrile-based fine fiber has an appropriate fineness, a number of wrinkles on the surface thereof, and a certain structural strength.
  • the acrylonitrile fiber nonwoven fabric separator of the present invention uses the above acrylonitrile fiber having a diameter of 0.5 ⁇ m to 2.0 ⁇ m to improve hydrophilicity and hold the electrolyte solution firmly.
  • the life characteristics of the battery can be set to a level equivalent to or higher than that of a conventional battery using a polyolefin fiber nonwoven fabric separator subjected to a hydrophilic treatment.
  • the diameter of the acrylonitrile-based fine fiber is preferably 0.8 ⁇ m to 1.6 ⁇ m.
  • acrylonitrile thick fibers having a diameter of 2.5 ⁇ m or more may be further used at the same time.
  • the structural strength of the separator is further improved, and the separator is less likely to be crushed, so that the life characteristics of the battery can be further improved.
  • the specific surface area of the acrylonitrile-based thick fibers is smaller than that of the acrylonitrile-based fine fibers, the surface wrinkles are relatively small.
  • the diameter of the acrylonitrile thick fiber is preferably 2.5 ⁇ m to 8.0 ⁇ m, and more preferably 2.5 ⁇ m to 7.5 ⁇ m.
  • the content of acrylonitrile fiber in the nonwoven fabric separator of acrylonitrile fiber of the present invention is acrylonitrile fiber. It is preferable that there is more content than.
  • the content of the acrylonitrile fine fiber in the nonwoven fabric separator of the acrylonitrile fiber is preferably 50% by mass to 100% by mass.
  • the content of the acrylonitrile fiber is preferably more than 0% by mass and 50% by mass or less.
  • a polyolefin fiber such as a polypropylene fiber having a known diameter of 2.0 ⁇ m to 5.0 ⁇ m may be used instead of the acrylonitrile thick fiber.
  • the performance of the obtained separator is good, but when the polyolefin fiber is a low hydrophilic fiber such as a polypropylene fiber that has not been hydrophilized, the polypropylene in the nonwoven fabric separator of acrylonitrile fiber is used. The fiber should not exceed 25% by weight, otherwise the separator performance will be degraded.
  • FIG. 1 is a perspective view schematically showing the structure of the lead storage battery of the present invention.
  • the lead storage battery 1 includes a battery case 2 and an electrode plate group 3 accommodated in the battery case 2.
  • the electrode plate group 3 is formed by laminating a plurality of positive electrodes 4 and a plurality of negative electrodes 5 with a separator 6 interposed therebetween.
  • the negative electrode 5 is located outside the electrode plate group 3, and the number thereof is one more than that of the positive electrode 4.
  • the positive electrode 4 is accommodated in a bag-shaped separator 6 a, and a chip-shaped separator 6 b is sandwiched between the bag-shaped separator 6 a and the negative electrode 5.
  • One end of the positive electrode connecting member 7 is connected to a plurality of positive electrodes 4, and the other end is connected to a positive electrode terminal (not shown) provided on the battery cap.
  • One end of the negative electrode connection member 8 is connected to the plurality of negative electrodes 5, and the other end is connected to a negative electrode terminal (not shown) provided on the battery cap.
  • a battery cap (not shown) is attached to the opening of the battery case 2.
  • a vent valve is provided at a liquid inlet provided in the battery cap, and this vent valve is used to discharge gas generated inside the battery to the outside of the battery.
  • the inventors of the present application produced three types of positive electrodes A, B, and C by changing the amount of acid used during the kneading of the positive electrode active material.
  • the pore distribution was measured by the mercury intrusion method.
  • the positive electrode C is a commonly used positive electrode and has a relatively large total pore volume (0.122 cm 3 / g). Since the positive electrodes B and A are sequentially reduced in the amount of acid during kneading, the numerical value of the total pore volume obtained is also decreasing in order, the pore volume of the positive electrode B is 0.110 cm 3 / g, The pore volume is 0.085 cm 3 / g.
  • the inventors of the present application prototyped several different types of negative electrodes by adding barium sulfate, lignin, and acetylene black at different contents to the negative electrode active material.
  • Batteries # 1 to # 8 were fabricated by combining the positive electrode C and the positive electrode B produced above with different negative electrodes. Table 1 shows specific parameters of the positive electrode and the negative electrode used in these batteries. These batteries were subjected to discharge tests at different discharge rates at ambient temperatures of 25 ° C. and ⁇ 15 ° C., respectively, and graphs shown in FIGS. 2A to 2B were created based on the test results.
  • the inventors of the present application further investigated the above phenomenon and obtained the following knowledge.
  • the discharge capacity decreases as the temperature decreases, and the discharge capacity tends to increase as the discharge rate decreases. This indicates that the ion diffusion of the electrolyte is affected by factors such as temperature and discharge rate, which affects the discharge performance of the battery.
  • the battery # 1 When compared with the battery # 2, the battery # 1 was superior in discharge capacity at room temperature (25 ° C.). This is because the electrolyte viscosity is low at room temperature, and the amount of electrolyte affects the battery discharge capacity. The larger the positive electrode pore volume, the greater the amount of electrolyte flowing to the positive electrode. It shows that it is more advantageous to improve performance. However, as the temperature decreases, as shown in FIG. 2B, the discharge capacities of the battery # 2 and the battery # 1 are basically in the same direction, and at this time, even if the pore volume of the positive electrode is increased. This indicates that the discharge capacity of the battery cannot be improved.
  • battery # 5 having a barium sulfate content of 4.2 mass% in the negative electrode active material is compared with battery # 2 having a barium sulfate content of 3.0 mass%.
  • the discharge capacity of battery # 5 was lower at room temperature (25 ° C.), but the discharge capacity of battery # 5 was somewhat higher than that of battery # 2 at low temperature ( ⁇ 15 ° C.). This indicates that barium sulfate can improve the charge / discharge characteristics of the negative electrode to some extent under low temperature conditions.
  • the inventors of the present application made a detailed study on the pore size distribution of the positive electrodes A, B and C. Based on the mercury intrusion method, the graph of the differential curve of the pore distribution of the positive electrode active material shown in FIG. 3 was obtained. And the integration process was performed with respect to the graph of the differential curve of FIG. 3, and the graph of the integral curve shown in FIG. 4 was obtained.
  • the positive electrode A having a total pore volume of 0.085 cm 3 / g of the positive electrode active material reaches a peak in the vicinity of a pore diameter of 0.09 ⁇ m. Means that the change rate of the pore volume at the pore diameter of 0.09 ⁇ m is the maximum.
  • a total pore volume for the positive electrode B of 0.110cm 3 / g see that the pore volume in the vicinity of a pore diameter 0.8 ⁇ m is peaked, the total pore volume of 0.122cm 3 / g Regarding the positive electrode C, it can be seen that the pore volume reaches a peak in the vicinity of the pore diameter of 2 ⁇ m.
  • the pore size distribution of the negative electrode active materials of the batteries # 1 to # 6 was similarly measured by the mercury intrusion method. The results are shown in FIG. Since the negative electrode active materials of the batteries # 7 and # 8 are the same as those of the battery # 6, illustration is omitted. As shown in FIG. 5, the pore volume of the negative electrode active material has two peaks in the vicinity of a pore diameter of 1.2 ⁇ m and 1.7 ⁇ m, respectively, but no peak exists in the vicinity of 0.8 ⁇ m.
  • the positive electrode B having a pore volume of 0.110 cm 3 / g has many pores having a pore diameter of 0.8 ⁇ m, and the specific pore diameter is suitable for the passage of sulfate ions at a low temperature.
  • the charge / discharge characteristics of the positive electrode can be improved.
  • the larger the total pore volume of the positive electrode active material the larger the pore volume peak in the differential curve shifts to the larger pore diameter. It can also be seen that the smaller the volume, the more the pore volume peak in the differential curve shifts to the smaller pore size.
  • the size of the total pore volume of the positive electrode active material reflects to some extent the size of the pore diameter of a large number of pores existing in the porous body of the positive electrode active material. Therefore, in the present invention, the pore volume of the positive electrode is appropriately reduced to fall within an appropriate range so that the porous body of the positive electrode active material is suitable for passing sulfate ions (around 0.8 ⁇ m). Have a large number of pores.
  • the total pore volume is too large, the amount of the electrolyte increases and the utilization rate of the positive electrode active material increases, but the adhesive force between the positive electrode active materials decreases, and the cycle life characteristics of the battery tend to decrease.
  • the total pore volume is too small, the electrolyte solution is too small and the movement of sulfate ions is hindered, the utilization rate of the positive electrode active material is lowered, and the cycle life characteristics tend to be lowered.
  • the total pore volume of the positive electrode active material is preferably in the range of 0.087 to 0.120 cm 3 / g, and may be in the range of 0.090 to 0.110 cm 3 / g. More preferred.
  • the total pore volume of the positive electrode active material it can be ensured that a large number of pores having a pore diameter of 0.8 ⁇ m are present in the positive electrode active material. Since the pores having the specific pore diameter are suitable for passing sulfate ions at a low temperature, it is easy to cause the positive electrode to perform a discharge reaction.
  • the fact that a large number of pores having a pore diameter of 0.8 ⁇ m are present in the positive electrode active material can be determined by a differential curve graph as shown in FIG. Specifically, in the graph of the differential curve showing the pore distribution of the positive electrode active material obtained by the mercury intrusion method, a peak appears in the pore volume in the vicinity of the pore diameter of 0.8 ⁇ m.
  • the 0.8 ⁇ m mentioned here includes the range of 0.2 ⁇ m before and after that, that is, the range of 0.6 to 1.0 ⁇ m, and preferably includes the range of 0.1 ⁇ m before and after that, that is, 0.7 to The range is 0.9 ⁇ m.
  • the fact that there are a large number of pores having a pore diameter of 0.8 ⁇ m in the positive electrode active material can be determined by a graph of an integral curve as shown in FIG.
  • the presence of a large number of pores having a pore diameter of 0.8 ⁇ m means that the pore volume having a pore diameter of 0.2 to 2.0 ⁇ m occupies 45% or more of the total pore volume, and more preferably It is 50% or more, and 55% or more is particularly preferable.
  • the size of the positive electrode pore volume also affects the cycle life of the battery.
  • the pore volume is too large, the mechanical strength of the electrode plate is lowered and the cycle life of the battery is shortened.
  • the mechanical strength of the positive electrode is increased, which is advantageous for improving the cycle life of the battery.
  • the negative electrode of the present invention it is preferable to add 3.2 to 4.8% by mass of barium sulfate as a nucleating agent with respect to the negative electrode active material. If the barium sulfate content is too high, the amount of the negative electrode active material is relatively reduced, and the structure becomes too dense, so that the charge acceptability at low temperatures is deteriorated, and the discharge capacity of the battery is also small. turn into. On the other hand, when the content of barium sulfate in the negative electrode active material is too small, the role as a nucleating agent cannot be fully exhibited, and the solidified lead lump becomes large, so that the charge acceptability is also lowered.
  • the range of the pore volume of the positive electrode and the range of the barium sulfate content in the negative electrode active material are in a specific combination, so that an excellent discharge capacity and charge acceptance can be obtained at low temperatures.
  • the conductivity of the negative electrode can be improved, and the discharge capacity, charge acceptance and cycle life characteristics of the lead-acid battery at low temperatures can be improved.
  • the acetylene black content in the negative electrode active material is preferably 0.3 to 2.0% by mass. When there is too little content of acetylene black, the electroconductivity of a negative electrode will worsen and charge / discharge performance will worsen. On the other hand, when there is too much content of acetylene black, there exists a problem that it is difficult to produce.
  • a lignin surfactant may be further added to the negative electrode active material.
  • lignin By adding lignin to the negative electrode active material, shrinkage of the negative electrode active material (Pb) can be prevented, and the cycle life of the battery can be further improved.
  • the content of the lignin surfactant in the negative electrode active material is not particularly limited, and may be, for example, 0 to 5% by mass, preferably 0.1 to 2.0% by mass, More preferably, it is 0.5 mass%. However, even if lignin is not added, practically sufficient cycle life characteristics can be obtained.
  • the electrode plate group is generally composed of 5 to 8 positive electrodes and 6 to 9 negative electrodes.
  • the inventors of the present application have a ratio of the total weight of the negative electrode active material applied to the negative electrode to the total weight of the positive electrode active material applied to the positive electrode (that is, the positive electrode active material). It has been found that there is an appropriate range in the weight ratio of the negative electrode active material to the negative electrode active material.
  • the weight ratio is preferably 0.7 to 0.95, and more preferably 0.75 to 0.90. The larger the weight ratio, the smaller the weight of the positive electrode active material relative to the negative electrode active material.
  • the weight ratio is larger than 0.95, the total pore volume of the positive electrode active material is too small, and the amount of the electrolyte flowing into the positive electrode is reduced, so that the discharge capacity of the battery itself is reduced.
  • the weight ratio is less than 0.7, the total pore volume of the positive electrode active material is too large, and most of the electrolyte flows into the positive electrode and less electrolyte flows into the negative electrode. And the low-temperature discharge capacity also decreases.
  • Example 1 (Preparation of positive electrode) An expanded lattice having an ear portion manufactured by the expanding method is defined as a positive electrode lattice (vertical: 137 mm, horizontal: 140 mm, thickness: 2.8 mm).
  • the lead powder (oxidation degree: about 80%) of raw material and sulfuric acid are mixed at a weight ratio of 100: 5 to obtain a lead paste, and 12% by mass of the lead powder of the raw material during kneading of the lead paste Water was added to obtain a positive electrode active material paste (hereinafter simply referred to as positive electrode lead paste).
  • the expanded grid was filled with 183.6 g of positive lead paste along the length of the grid. Thereafter, the grid filled with the lead paste was cut into a predetermined size and shape, and aged and dried to obtain an unformed positive electrode (vertical: 137 mm, horizontal: 140 mm).
  • An expanded lattice having an ear portion manufactured by the expanding method is defined as a negative electrode lattice (vertical: 137 mm, horizontal: 140 mm, thickness: 1.8 mm).
  • raw material lead powder oxidation degree: about 80%
  • water oxidation degree: about 80%
  • sulfuric acid were mixed at a weight ratio of 100: 11: 2.
  • negative electrode lead paste 4.2% by mass of barium sulfate (manufactured by Qingdao Dongfeng Chemical Co., Ltd.), 0.2% by mass of lignin (sodium lignin sulfonate, manufactured by Sanmic Shoji Co., Ltd.) as an expanding agent and 1% by mass as a conductive material % Of acetylene black (manufactured by Kanka Chemical Co., Ltd.) was added and kneaded to obtain a negative electrode active material paste (hereinafter simply referred to as negative electrode lead paste).
  • barium sulfate manufactured by Qingdao Dongfeng Chemical Co., Ltd.
  • lignin sodium lignin sulfonate, manufactured by Sanmic Shoji Co., Ltd.
  • a conductive material % Of acetylene black manufactured by Kanka Chemical Co., Ltd.
  • the seven positive electrodes obtained as described above were inserted into seven bag-shaped separators made of acrylonitrile-based fiber nonwoven fabric subjected to hydrophilic treatment, and alternately with the eight negative electrodes obtained as described above.
  • an electrode plate group was obtained by inserting a chip-like separator made of glass fiber between the bag-like separator and the negative electrode.
  • the ears of the electrode plates of the same polarity were welded to the connecting members to form bus bars. Thereafter, the electrode plate groups were accommodated one by one in six single cell tanks partitioned by partition walls in the battery case.
  • the pore volume of the positive electrode was measured by the mercury intrusion method in the following steps. First, after the battery produced as described above was fully charged, the battery was disassembled and the electrode plate group was taken out of the battery, and the electrode plate group was divided into a positive electrode, a negative electrode, and a separator. The positive electrode and the negative electrode were immersed in water to remove the sulfuric acid component contained in the electrode plate, and then the positive electrode and the negative electrode were dried. At this time, the negative electrode was dried in vacuum. A predetermined amount of the active material was weighed from the dried electrode plate and measured with a mercury intrusion porosimeter (manufactured by Micromeritics, AutoPore III9410 type fully automatic mercury intrusion porosimeter).
  • the pore volume of the positive electrode in the battery of Example 1 measured by the above steps was 0.087 cm 3 / g. According to the graph of the differential curve of the pore distribution, pores having a pore diameter of 0.8 ⁇ m were present in the positive electrode active material. It was confirmed that a relatively large number existed.
  • Example 2 The amount of water added was changed in the kneading of the positive electrode lead paste so that the pore volume of the positive electrode obtained was 0.110 cm 3 / g. Otherwise, a positive electrode was produced in the same manner as in Example 1, and a negative electrode and a lead storage battery were produced in the same manner as in Example 1. It was confirmed by the graph of the differential curve of the pore distribution that there were many pores having a pore diameter of 0.8 ⁇ m in the positive electrode active material.
  • Example 3 The amount of water added was changed in the kneading of the positive electrode lead paste so that the pore volume of the positive electrode obtained was 0.120 cm 3 / g. Otherwise, a positive electrode was produced in the same manner as in Example 1, and a negative electrode and a lead storage battery were produced in the same manner as in Example 1. It was confirmed by the graph of the differential curve of the pore distribution that there were many pores having a pore diameter of 0.8 ⁇ m in the positive electrode active material.
  • Comparative Example 1 The amount of water added in the kneading of the positive electrode lead paste was changed so that the pore volume of the positive electrode obtained was 0.085 cm 3 / g. Otherwise, a positive electrode was produced in the same manner as in Example 1, and a negative electrode and a lead storage battery were produced in the same manner as in Example 1. From the graph of the differential curve of the pore distribution, it was confirmed that there were very few pores having a pore diameter of 0.8 ⁇ m in the positive electrode active material.
  • Comparative Example 2 The amount of water added in the kneading of the positive electrode lead paste was changed so that the pore volume of the positive electrode obtained was 0.122 cm 3 / g. Otherwise, a positive electrode was produced in the same manner as in Example 1, and a negative electrode and a lead storage battery were produced in the same manner as in Example 1. It was confirmed by the graph of the differential curve of the pore distribution that relatively few pores having a pore diameter of 0.8 ⁇ m were present in the positive electrode active material.
  • Example 4 In production of the negative electrode, the barium sulfate content in the negative electrode active material was changed to 3.2 mass%. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 5 In preparation of the negative electrode, the barium sulfate content in the negative electrode active material was changed to 4.8% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Comparative Example 3 In production of the negative electrode, the barium sulfate content in the negative electrode active material was changed to 3% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Comparative Example 4 In production of the negative electrode, the barium sulfate content in the negative electrode active material was changed to 5% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 6 In the production of the negative electrode, the acetylene black content in the negative electrode active material was changed to 0.3% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 7 In preparation of the negative electrode, the acetylene black content in the negative electrode active material was changed to 0.5% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 8 In preparation of the negative electrode, the acetylene black content in the negative electrode active material was changed to 1.5% by mass. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 9 In preparation of the negative electrode, the acetylene black content in the negative electrode active material was changed to 2.0 mass%. Otherwise, a negative electrode was produced in the same manner as in Example 2, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2. In this example, since the content of acetylene black was large, battery production was relatively difficult.
  • Example 10 In the production of the negative electrode, a negative electrode was produced in the same manner as in Example 2 except that lignin was not added to the negative electrode active material, and a positive electrode and a lead storage battery were produced in the same manner as in Example 2.
  • Example 11 The weight ratio of the negative electrode / positive electrode active material was changed to 0.7, and a positive electrode, a negative electrode, and a lead storage battery were fabricated in the same manner as in Example 2 except that.
  • Example 12 The weight ratio of the negative electrode / positive electrode active material was changed to 0.75, and a positive electrode, a negative electrode, and a lead storage battery were produced in the same manner as in Example 2 except that.
  • Example 13 The weight ratio of the negative electrode / positive electrode active material was changed to 0.9, and a positive electrode, a negative electrode, and a lead storage battery were produced in the same manner as in Example 2 except that.
  • Example 14 The weight ratio of the negative electrode / positive electrode active material was changed to 0.95, and a positive electrode, a negative electrode, and a lead storage battery were fabricated in the same manner as in Example 2 except that.
  • discharge capacity (1) The fully charged battery was left at 0 ° C. for 10 hours or more, and discharged at a constant current of 0.25 C until the voltage dropped to 10.5 V. Ambient temperature was kept at 0 ° C. The discharge capacity at this time is referred to as “discharge capacity (1)”. Subsequently, charging was performed at a constant voltage of 14.7 V at 0 ° C. The maximum current was 0.3 C and the battery was charged for 10 hours. Thereafter, discharging was performed at 0 ° C. with a constant current of 0.25 C until the voltage dropped to 10.5 V. The discharge capacity at this time is referred to as “discharge capacity (2)”.
  • the charge acceptability of the battery at low temperature was calculated by the following formula, and the charge acceptability was evaluated according to the following criteria.
  • Charge acceptance (%) Discharge capacity (2) / Discharge capacity (1) x 100% Evaluation criteria: Charge acceptability is 100%: Indicates that the performance is particularly excellent Charge acceptability is 90% or more and less than 100%: Indicates that the performance is good Charge acceptability is 80% or more and less than 90%: Performance is normal Although it indicates that it is practical, the charge acceptance is less than 80%: it indicates that it has not reached the practical level. (2) Low-temperature discharge capacity The low-temperature discharge capacity of the battery was measured in the following steps.
  • the fully charged battery was left in an environment of ⁇ 15 ° C. within 1 hour after the completion of charging and left for 10 hours or more, and discharged at a current of I 20 (5 A).
  • the ambient temperature of the battery was kept at -15 ° C.
  • the discharge was stopped and the discharge time was recorded.
  • the battery discharge capacity at low temperature was calculated according to the following formula, and the low temperature discharge capacity was evaluated according to the following criteria.
  • Low temperature discharge capacity (Ah) discharge current (A) ⁇ discharge time (h) Evaluation criteria: Low temperature discharge capacity of 70 Ah or more: Indicates that the performance is particularly excellent Low temperature discharge capacity of 65 Ah or more and less than 70 Ah: Indicates that the performance is good Low temperature discharge capacity of 60 Ah or more and less than 65 Ah: Performance is normal, but practical The low-temperature discharge capacity is less than 60 Ah, indicating that it is not possible. (3) Cycle life characteristics For each lead storage battery obtained in Examples 1 to 14 and Comparative Examples 1 to 4, A cycle life test was conducted under the following conditions.
  • the battery cycle life was evaluated according to the following criteria.
  • Cycle number of 500 or more Indicates that the performance is particularly excellent Cycle number of 400 or more and less than 500: Indicates that the performance is satisfactory Cycle number of 200 or more and less than 400: Performance is normal, but is practical The number of cycles is less than 200: it indicates that it has not reached the practical level.
  • Table 2 Various parameters and battery performance tests and evaluation results for each of the above storage batteries are summarized in Table 2 below.
  • the battery of Comparative Example 1 has very few pores having a pore diameter of 0.8 ⁇ m, and the positive electrode has a pore volume of 0.085 cm 3 / g, which is the lower limit of the preferred range of the pore volume in the present invention. Since the amount of electrolyte is small and the diffusion resistance of sulfate ions is large, it can be seen that the discharge capacity of the battery is small and the charge acceptance at low temperatures is also poor.
  • the battery of Comparative Example 2 also has very few pores having a pore diameter of 0.8 ⁇ m, and the positive electrode has a pore volume of 0.122 cm 3 / g, which exceeds the upper limit of the preferred range of the pore volume in the present invention.
  • the positive electrode pore volume (0.110 cm 3 / g) is within the preferred range of the present invention, but the barium sulfate content (3.0% by mass) in the negative electrode active material. Is below the lower limit of the range in the present invention. Therefore, since there is too little barium sulfate and the mass of the solidified negative electrode active material becomes large, the low-temperature charge acceptance is low, the balance of the discharge characteristics between the positive and negative electrodes is poor, and the low-temperature discharge capacity of the battery is also small. .
  • the barium sulfate content (5.0% by mass) in the negative electrode active material is The upper limit of the range in the present invention is exceeded. Therefore, since there is too much barium sulfate, the amount of the negative electrode active material becomes relatively small, and the structure becomes too dense, the charge acceptability at low temperatures is deteriorated, and the discharge capacity of the battery is also reduced.
  • the pore volume of the positive electrode is within the range of the present invention (0.087cm 3 /g ⁇ 0.120cm 3 / g) , and barium sulfate content of the anode active material Is within the range of the present invention (3.2 to 4.8% by mass), so the discharge characteristic balance between the positive and negative electrodes is good, and it is excellent in all aspects of low-temperature charge acceptance, low-temperature discharge capacity, and cycle life. The effect was obtained.
  • the weight ratio of the negative electrode active material to the positive electrode active material is within the range of 0.7 to 0.95, more preferably within the range of 0.75 to 0.90. It can be seen that the balance of charge and discharge characteristics between the negative electrodes can be strengthened, and a more remarkable effect can be obtained.
  • the lead acid battery of the present invention not only has good cycle life characteristics, but also has excellent discharge capacity and charge acceptance at low temperatures. Especially, the lead acid battery for energy storage in a natural energy system such as solar energy. Suitable for use.

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