WO2019021691A1 - 鉛蓄電池 - Google Patents

鉛蓄電池 Download PDF

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Publication number
WO2019021691A1
WO2019021691A1 PCT/JP2018/023256 JP2018023256W WO2019021691A1 WO 2019021691 A1 WO2019021691 A1 WO 2019021691A1 JP 2018023256 W JP2018023256 W JP 2018023256W WO 2019021691 A1 WO2019021691 A1 WO 2019021691A1
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Prior art keywords
carbon material
negative electrode
lead
electrode plate
lead storage
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PCT/JP2018/023256
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English (en)
French (fr)
Japanese (ja)
Inventor
賢治 山内
絵里子 佐々木
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株式会社Ｇｓユアサ
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Application filed by 株式会社Ｇｓユアサ filed Critical 株式会社Ｇｓユアサ
Priority to CN201880048517.4A priority Critical patent/CN110998924B/zh
Priority to JP2019532439A priority patent/JP7111099B2/ja
Priority to DE112018003776.2T priority patent/DE112018003776T5/de
Publication of WO2019021691A1 publication Critical patent/WO2019021691A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative 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

Definitions

  • the present invention relates to a lead storage battery.
  • Lead storage batteries are used in a variety of applications in addition to automotive and industrial applications.
  • the lead storage battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution.
  • the negative electrode plate contains a negative electrode material.
  • a carbon material is added to the negative electrode material.
  • PSOC partial charge state
  • ISS idling stop / start
  • a lead storage battery is required to be excellent in life performance (hereinafter referred to as PSOC life performance) in charge and discharge cycles under PSOC conditions.
  • Patent Document 1 proposes that carbon black be added to a negative electrode plate as a carbon material in order to improve PSOC life performance.
  • the lead storage battery includes a negative electrode plate, a positive electrode plate, and an electrolyte solution.
  • the negative electrode plate includes a negative electrode material containing a carbon material,
  • the carbon material includes a first carbon material having a particle size of 32 ⁇ m or more, and a second carbon material having a particle size of less than 32 ⁇ m,
  • the ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less
  • the present invention relates to a lead storage battery, in which a porous layer is disposed between the negative electrode plate and the positive electrode plate.
  • the lead storage battery includes a negative electrode plate, a positive electrode plate, and an electrolytic solution.
  • the negative electrode plate includes a negative electrode material containing a carbon material, and the carbon material includes a first carbon material having a particle size of 32 ⁇ m or more and a second carbon material having a particle size of less than 32 ⁇ m.
  • the ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less.
  • a porous layer is disposed between the negative electrode plate and the positive electrode plate.
  • the powder resistance of the powder material is known to change due to the shape of the particles, the particle size, the internal structure of the particles, and / or the crystallinity of the particles.
  • the powder resistance of the carbon material is not directly related to the resistance of the negative electrode plate, and is not considered to affect the PSOC life performance.
  • the first carbon material and the second carbon material having different particle sizes are used in combination, and the powder resistance ratio R2 / R1 of the first carbon material to the second carbon material is 15 to 15
  • the powder resistance ratio R2 / R1 of the first carbon material to the second carbon material is 15 to 15
  • the negative electrode active material When a conductive network is formed in the negative electrode material, the negative electrode active material is easily oxidized during discharge at a portion (near the carbon material) where the resistance is low in the negative electrode plate, and the surface of the negative plate is charged during charging.
  • the lead ion contained in the electrolytic solution is reduced at this time, metal lead is easily deposited, and metal lead dendrite is easily grown.
  • the porous layer is disposed between the negative electrode plate and the positive electrode plate. This suppresses the osmotic short circuit caused by the growth of metallic lead dendrites.
  • the internal resistance is increased. Therefore, according to conventional technical common sense, it is considered that the PSOC life performance declines when the porous layer is disposed.
  • the negative electrode plate and the positive electrode plate by using the first carbon material and the second carbon material while controlling the powder resistance ratio R2 / R1 in the range of 15 to 155, the negative electrode plate and the positive electrode plate.
  • the deterioration of PSOC life performance is suppressed. It is presumed that this is because the conductive network is easily formed in the negative electrode material by using the first carbon material and the second carbon material in combination.
  • positioning a porous layer stratification of electrolyte solution is suppressed. This is also presumed to be one of the factors for suppressing the decrease in PSOC life performance.
  • the specific surface area ratio S2 / S1 or porous layer described later is controlled while controlling the powder resistance ratio R2 / R1 in the range of 15 to 155.
  • the charge acceptance performance can also be improved by adjusting the thickness and the like.
  • a woven or non-woven fabric can be used for the porous layer.
  • the non-woven fabric is a mat in which fibers are not woven but entangled.
  • Woven or non-woven fabrics are mainly made of fibers.
  • 60% by mass or more of the porous layer is formed of fibers.
  • Glass fibers, polymer fibers (polyolefin fibers, acrylic fibers, polyester fibers such as polyethylene terephthalate fibers, etc.), pulp fibers, etc. can be used as fibers constituting the woven or non-woven fabric.
  • glass fiber for example, non-woven fabric containing glass fiber is preferable.
  • the non-woven fabric containing glass fiber has the same electrical resistance and density as the non-woven fabric containing polyethylene-based fiber, and is relatively inexpensive and easy to manufacture.
  • the woven or non-woven fabric may contain components other than fibers, such as an acid-resistant inorganic powder, a polymer as a binder, and the like.
  • the porous layer may be disposed on the surface of the negative electrode plate or may be disposed on the surface of the positive electrode plate, but is preferably disposed on the surface of the negative electrode plate from the viewpoint of suppressing the growth of dendrites.
  • a method of arranging the porous layer for example, a woven or non-woven fabric is laminated on the surface of a negative electrode plate or a positive electrode plate, or a bag formed of woven or non-woven fabric is prepared It can be stored in the A woven fabric or a non-woven fabric may be attached to a separator described later.
  • porous layer faces one surface of the negative electrode plate or the positive electrode plate, and the other surface of the porous layer faces one surface of the later-described separator.
  • the porous layer is formed of a woven or non-woven fabric and the separator is formed of a microporous film described later, the porous surface is in a region where the other surface of the porous layer and one surface of the separator described later face each other.
  • the holes in the layer and the holes in the separator do not communicate with each other. Therefore, the growth of dendrite from the negative electrode plate to the positive electrode plate is suppressed also in the region.
  • the porous layer may be composed of a single woven or non-woven fabric, or a plurality of woven or non-woven fabrics may be stacked.
  • the thickness of the porous layer is, for example, 5 ⁇ m or more and less than 600 ⁇ m.
  • the thickness of a porous layer is the thickness at the time of 19.6 KPa pressurization in the dry state which does not contain electrolyte solution.
  • the thickness of the porous layer can be determined by the following procedure.
  • the lead storage battery is disassembled, the porous layer is taken out, the sulfuric acid is removed by washing with water, and dried. Thereafter, 10 porous layers of 50 mm ⁇ 50 mm are stacked to form a laminate, the thickness T of the laminate at 19.6 KPa pressure is measured, and the value of T / 10 is a porous layer. It calculates as thickness of 1 per sheet.
  • the thickness of a porous layer is 10 micrometers or more and 500 micrometers or less from a viewpoint of permeation short circuit control.
  • the thickness of the porous layer is 10 ⁇ m or more, the effect of suppressing the osmotic short circuit by providing the porous layer is further enhanced.
  • the thickness of the porous layer is 500 ⁇ m or less, an increase in internal resistance due to the arrangement of the porous layer and a decrease in battery performance (such as PSOC life performance and charge acceptance performance) due to the increase are suppressed.
  • the thickness of a porous layer is 500 micrometers or less, the space which arrange
  • the thickness of the porous layer is more preferably 100 ⁇ m or more and 500 ⁇ m or less.
  • the electrical resistance of the porous layer is, for example, less than 0.0015 ⁇ ⁇ dm 2 / sheet.
  • the density of the porous layer is, for example, 0.15 to 1.5 g / cm 3 .
  • the average fiber diameter of the glass fiber is, for example, about 10 to 20 ⁇ m.
  • the carbon material includes a first carbon material having a particle size of 32 ⁇ m or more and a second carbon material having a particle size of less than 32 ⁇ m.
  • the first carbon material and the second carbon material are separated and distinguished in the procedure described later.
  • each carbon material examples include carbon black, graphite, hard carbon, soft carbon and the like.
  • carbon black examples include acetylene black, ketjen black, furnace black, lamp black and the like.
  • the graphite may be any carbon material containing a graphite type crystal structure, and may be any of artificial graphite and natural graphite.
  • the intensity of a peak appearing in 1300 cm -1 or 1350 cm -1 or less in the range of the Raman spectrum (D band) and 1550 cm -1 or 1600 cm -1 peak appearing in the range (G band) of the first carbon material Graphite is one having a ratio I D / I G of 0 or more and 0.9 or less.
  • the ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less.
  • the powder resistance ratio R2 / R1 can be adjusted by changing the type, particle diameter, specific surface area, and / or aspect ratio of each carbon material used to produce the negative electrode material.
  • the first carbon material for example, at least one selected from the group consisting of graphite, hard carbon, and soft carbon is preferable.
  • the first carbon material preferably contains at least graphite.
  • the second carbon material preferably contains at least carbon black. When these carbon materials are used, the powder resistance ratio R2 / R1 can be easily adjusted.
  • the powder resistance ratio R2 / R1 is preferably 15 or more and 85 or less. In this case, while the high PSOC life performance is maintained, the charge acceptance performance is further improved, and the occurrence of the osmotic short circuit is further suppressed.
  • the ratio S2 / S1 of the specific surface area S2 of the second carbon material to the specific surface area S1 of the first carbon material is, for example, 10 or more and 400 or less.
  • the specific surface area ratio S2 / S1 is preferably 20 or more, and more preferably 110 or more. Moreover, it is preferable that it is 240 or less. These upper limits and lower limits can be arbitrarily combined.
  • the specific surface area ratio S2 / S1 is 20 or more, a large number of contact points between the carbon material and the negative electrode active material can be secured, and the charge acceptance performance can be enhanced even when the porous layer is disposed.
  • the specific surface area ratio S2 / S1 is 20 or more and 240 or less, in the preparation of the negative electrode plate, a negative electrode paste having good properties is obtained, and the filling property of the negative electrode paste to the negative electrode current collector is improved. The reliability of the battery can be improved. From the viewpoint of further enhancing the charge acceptance performance, the specific surface area ratio S2 / S1 is more preferably 110 or more and 240 or less.
  • the average aspect ratio of the first carbon material is, for example, 1 or more and 200 or less.
  • the average aspect ratio of the first carbon material is preferably 1 or more, more preferably 1.5 or more. Moreover, Preferably it is 100 or less, More preferably, it is 30 or less. These upper limits and lower limits can be arbitrarily combined.
  • PSOC life performance is further enhanced. It is considered that this is because when the average aspect ratio is in such a range, the conductive network is easily formed in the negative electrode material and the formed conductive network is easily maintained.
  • the average aspect ratio of the first carbon material when the average aspect ratio of the first carbon material is 1.5 or more, the outflow of the carbon material to the electrolyte due to the repetition of charge and discharge is suppressed, so the effect of improving the PSOC life performance is further increased. be able to.
  • the average aspect ratio of the first carbon material when the average aspect ratio of the first carbon material is 30 or less, the adhesion between the active material particles can be easily secured, so the generation of cracks in the negative electrode plate can be suppressed, and the deterioration of PSOC life performance can be suppressed.
  • the average aspect ratio of the first carbon material When the average aspect ratio of the first carbon material is 1.5 or more, the larger the average aspect ratio of the first carbon material, the easier it is for an osmotic short circuit to occur. This is because, as the average aspect ratio of the first carbon material increases, the area ratio of the first carbon material exposed on the surface of the negative electrode plate increases, and metallic lead dendrite grows near the low resistance first carbon material. It is presumed that it is because it becomes easy. Therefore, when the average aspect ratio of the first carbon material is 1.5 or more, the effect of suppressing the osmotic short circuit by providing the porous layer is significantly obtained.
  • the content of the first carbon material in the negative electrode material is, for example, 0.05% by mass or more and 3.0% by mass or less. Preferably it is 0.1 mass% or more. Moreover, Preferably it is 2.0 mass% or less, More preferably, it is 1.5 mass% or less. These upper limits and lower limits can be arbitrarily combined.
  • the content of the first carbon material is 0.05% by mass or more, the effect of improving the PSOC life performance can be further enhanced.
  • the content of the first carbon material is 3.0% by mass or less, the adhesion between the active material particles is easily secured, so the occurrence of cracks in the negative electrode plate is suppressed, and the high PSOC life performance is further secured. It will be easier.
  • the content of the second carbon material in the negative electrode material is, for example, 0.03% by mass or more and 3.0% by mass or less. Preferably it is 0.05 mass% or more. Moreover, Preferably it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less. These upper limits and lower limits can be arbitrarily combined. When the content of the second carbon material in the negative electrode material is 0.03% by mass or more and 3.0% by mass or less, PSOC life performance can be further enhanced.
  • the content of each carbon material in the negative electrode material is determined by the procedure of (A-1) described later.
  • A Analysis of carbon material
  • A-1 Separation of carbon material Dissolve a fully charged lead storage battery of formation, take out the negative electrode plate, remove sulfuric acid by washing with water, and vacuum dry (under pressure lower than atmospheric pressure) To dry). Next, the negative electrode material is collected from the dried negative electrode plate and pulverized. To 5 g of the crushed sample, 30 mL of a 60% by mass nitric acid aqueous solution is added and heated at 70 ° C.
  • the remaining carbon material on the sieve is used as the first carbon material without passing through the sieve eyes, and the sieve eyes are passed.
  • the thing be the second carbon material. That is, the particle size of each carbon material is based on the size of the sieve openings.
  • JIS Z 8815 1994.
  • the carbon material is placed on a sieve with an opening of 32 ⁇ m and sieved by gently shaking the sieve for 5 minutes while sprinkling ion exchange water.
  • the first carbon material remaining on the sieve is collected from the sieve by flowing ion exchange water, and separated from the ion exchange water by filtration.
  • the second carbon material passed through the sieve is recovered by filtration using a nitrocellulose membrane filter (0.1 ⁇ m mesh).
  • the recovered first and second carbon materials are each dried at a temperature of 110 ° C. for 2 hours.
  • the sieve with a mesh size of 32 ⁇ m one provided with a sieve screen having a nominal mesh size of 32 ⁇ m as defined in JIS Z 8801-1: 2006 is used.
  • content of each carbon material in a negative electrode material measures the mass of each carbon material isolate
  • the fully charged state of the lead storage battery means, in the case of a liquid battery, constant current charging in a water tank at 25 ° C. until current reaches 0.2 V / cell at a current of 0.2 CA. In addition, constant current charging is performed for 2 hours at 0.2 CA.
  • the fully charged state means constant current constant voltage charging of 2.23 V / cell at 0.2 CA in a 25 ° C. air tank, and charging current at constant voltage charging When it becomes 1 mCA or less, it is in the state where charging was finished.
  • 1CA is a current value (A) of the same numerical value as the nominal capacity (Ah) of the battery. For example, for a battery with a nominal capacity of 30 Ah, 1CA is 30A and 1mCA is 30mA.
  • the powder resistance R1 of the first carbon material and the powder resistance R2 of the second carbon material are the first carbon material and the first carbon material separated in the procedure of the above (A-1).
  • a powder resistance measurement system MCP-PD51 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • the pressure is 3.18 MPa under JIS K 7194: 1994. It is a value measured by the four-point probe method using a low resistance resistivity meter (Loresta-GX MCP-T700, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to the standard.
  • the specific surface area s1 of the first carbon material and the specific surface area s2 of the second carbon material are the BET specific surface areas of the first carbon material and the second carbon material, respectively.
  • the BET specific surface area can be determined by a gas adsorption method using a BET equation, using each of the first carbon material and the second carbon material separated in the procedure of the above (A-1).
  • Each carbon material is pretreated by heating in nitrogen flow at a temperature of 150 ° C. for 1 hour. Using the pretreated carbon material, the BET specific surface area of each carbon material is determined by the following apparatus under the following conditions.
  • Measuring device Micromeritics TriStar 3000 Adsorption gas: Nitrogen gas with a purity of 99.99% or higher Adsorption temperature: Liquid nitrogen boiling point temperature (77 K) Calculation method of BET specific surface area: According to 7.2 of JIS Z 8830: 2013
  • A-4) Average Aspect Ratio of First Carbon Material The first carbon material separated in the above procedure (A-1) is observed with an optical microscope or an electron microscope, and 10 or more arbitrary particles are selected. , Take a magnified picture of it. Next, the photograph of each particle is subjected to image processing to obtain the maximum diameter d1 of the particle and the maximum diameter D2 in the direction orthogonal to the maximum diameter d1 and dividing the d1 by d2 to obtain the aspect ratio of each particle Ask. The average aspect ratio is calculated by averaging the obtained aspect ratios.
  • the organic flameproofing agent contained in the negative electrode material is an organic polymer containing a sulfur element, and generally contains one or more, preferably a plurality of aromatic rings in the molecule, and also contains a sulfur element as a sulfur-containing group There is.
  • the sulfur-containing groups the sulfonic acid or sulfonyl group, which is a stable form, is preferred.
  • the sulphonic acid groups may be present in acid form or in salt form as Na salts.
  • lignin may be used, or a synthetic organic plasticizer may be used.
  • a synthetic organic flameproofing agent a condensate of formaldehyde with an aromatic compound having a sulfur-containing group may be used.
  • lignin include lignin, lignin derivatives such as lignin, lignin sulfonic acid or salts thereof (alkali metal salts such as sodium salts and the like), and the like.
  • the organic plasticizers may be used alone or in combination of two or more.
  • lignin and a condensate of an aromatic compound having a sulfur-containing group with formaldehyde may be used in combination.
  • the aromatic compound bisphenols, biphenyls, naphthalenes and the like are preferably used.
  • the negative electrode plate of the lead storage battery contains a negative electrode material.
  • the negative electrode plate can usually be composed of a negative electrode current collector (negative electrode grid) and a negative electrode material.
  • the negative electrode material is obtained by removing the negative electrode current collector from the negative electrode plate.
  • matte and pasting paper may be stuck on the negative electrode plate.
  • the negative electrode plate includes such a member (sticking member)
  • the negative electrode material is one obtained by removing the negative electrode current collector and the sticking member.
  • the thickness of the electrode plate is a thickness including a mat. When a mat is attached to the separator, the thickness of the mat is included in the thickness of the separator.
  • the negative electrode material contains a negative electrode active material (lead or lead sulfate) which exhibits a capacity by a redox reaction.
  • the negative electrode active material in a charged state is cancellous lead, but an unformed negative electrode plate is usually produced using lead powder.
  • the negative electrode material contains a carbon material.
  • the negative electrode material may optionally contain other additives such as an organic plasticizer, barium sulfate and the like.
  • the content of the organic anti-shrinkage agent contained in the negative electrode material is the content in the negative electrode material collected by the method described later from the already-formed fully charged lead-acid battery.
  • the content of barium sulfate in the negative electrode material is, for example, preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and may be 0.5% by mass or more, or 1.0% by mass or more. 1.3 mass% or more may be sufficient. On the other hand, 3.0 mass% or less is preferable, 2.5 mass% or less is more preferable, and 2 mass% or less is still more preferable. These lower limit value and upper limit value can be arbitrarily combined.
  • the method for determining the amount of the organic plasticizer and the barium sulfate contained in the negative electrode material will be described.
  • the lead storage battery after formation is fully charged and then disassembled to obtain an anode plate to be analyzed.
  • the obtained negative electrode plate is subjected to water washing and drying to remove the electrolyte solution in the negative electrode plate.
  • the negative electrode material is separated from the negative electrode plate to obtain an uncrushed initial sample.
  • Infrared spectrum of powder to be analyzed UV-visible absorption spectrum of solution obtained by dissolving powder to be analyzed in distilled water etc.
  • NMR spectrum of solution obtained by dissolving powder to be analyzed in solvent such as heavy water NMR spectrum of solution obtained by dissolving powder to be analyzed in solvent such as heavy water
  • the UV-visible absorption spectrum of the filtrate to be analyzed is measured.
  • the content of the organic plasticizer in the negative electrode material is quantified using the spectrum intensity and the calibration curve prepared in advance. If the structural formula of the organic flameproofing agent to be analyzed can not be specified exactly and the calibration curve of the same organic flameproofing agent can not be used, UV-visible absorption spectrum, infrared spectrum, similar to the organic flameproofing agent to be analyzed A calibration curve is prepared using an available organic plasticizer which exhibits NMR spectra and the like.
  • the obtained solid content is dispersed in water to form a dispersion, and the carbonaceous material and components other than barium sulfate (for example, a reinforcing material) are removed from the dispersion using a sieve.
  • the dispersion is subjected to suction filtration using a pre-measured membrane filter, and the membrane filter is dried in a dryer at 110 ° C. together with the filtered sample.
  • the filtered sample is a mixed sample of a carbonaceous material and barium sulfate.
  • the mass of the mixed sample (A) is measured by subtracting the mass of the membrane filter from the total mass of the dried mixed sample and the membrane filter.
  • the dried mixed sample is placed in a crucible together with a membrane filter and subjected to flame ashing at 700 ° C. or higher.
  • the remaining residue is barium oxide.
  • the mass of barium oxide is converted to the mass of barium sulfate to determine the mass (B) of barium sulfate.
  • the negative electrode current collector may be formed by casting of lead (Pb) or lead alloy, or may be formed by processing a lead or lead alloy sheet. Examples of the processing method include expand processing and punching processing.
  • the lead alloy used for the negative electrode current collector may be any of a Pb—Sb based alloy, a Pb—Ca based alloy, and a Pb—Ca—Sn based alloy. These lead or lead alloys may further contain at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, Cu and the like as an additive element.
  • the negative electrode plate can be formed by filling a negative electrode current collector with a negative electrode paste, ripening and drying to prepare an unformed negative electrode plate, and then forming the unformed negative electrode plate.
  • the negative electrode paste is prepared by adding water and sulfuric acid to lead powder, a carbon material, and, if necessary, various additives, and kneading.
  • a synthetic fiber etc. When adding a reinforcing material, a synthetic fiber etc. can be used. From the viewpoint of acid resistance and mechanical strength, fibers of polyolefin type, polyacrylic type, polyester type and the like can be used, and those having a straight shape, a shape having a bend, a shape such as a crimped shape can be used. It is preferable to use one having a fiber length of 0.5 to 20 mm. The diameter of the fibers is preferably 10 to 50 ⁇ m, more preferably 10 to 35 ⁇ m. It is preferable that 0.01 to 2 mass% be contained in the electrode material.
  • the formation can be performed by charging in a state where the unformed negative electrode plate is immersed in an electrolyte solution containing sulfuric acid.
  • the formation may be carried out in the battery case after the assembly of the lead storage battery, or a formation formation tank containing an electrolytic solution may be prepared separately and may be performed before the assembly of the lead storage battery or the electrode plate group.
  • the positive electrode plate of the lead storage battery is classified into a paste type and a clad type.
  • the paste type positive electrode plate comprises a positive electrode current collector and a positive electrode material.
  • the positive electrode material is held by the positive electrode current collector.
  • the positive electrode current collector may be formed in the same manner as the negative electrode current collector, and can be formed by casting of lead or lead alloy or processing of lead or lead alloy sheet.
  • the clad positive electrode plate comprises a plurality of porous tubes, a cored bar inserted in each tube, a current collecting portion connecting the cored bar, and a positive electrode material filled in the tube in which the cored bar is inserted. And a hinge connecting a plurality of tubes.
  • the core metal and the current collector connecting the core metal are collectively called a positive electrode current collector.
  • Examples of lead alloys used for the positive electrode current collector include Pb—Ca alloys, Pb—Sb alloys, and Pb—Ca—Sn alloys.
  • the lead alloy may further contain, as an additive element, at least one selected from the group consisting of Ba, Ag, Al, Bi, As, Se, and Cu.
  • the positive electrode current collector may have lead alloy layers different in composition, and a plurality of alloy layers may be provided.
  • As the core metal Pb—Ca based alloy, Pb—Sb based alloy, etc. are used.
  • the positive electrode material contains a positive electrode active material (lead dioxide, lead sulfate, lead monoxide) that develops a capacity by a redox reaction.
  • the positive electrode material may optionally contain other additives.
  • the unformed paste type positive electrode plate is obtained by filling a positive electrode current collector with a positive electrode paste prepared by adding lead powder, various additives, water, and sulfuric acid, and ripening and drying. When ripening, it is preferable to ripen the unformed positive electrode plate at a temperature higher than room temperature and high humidity. Thereafter, the unformed positive electrode plate is formed.
  • the clad positive electrode plate is formed by filling a tube into which a core metal is inserted with lead powder or lead powder in a slurry form, and bonding a plurality of tubes in a coordinated manner.
  • a separator is usually disposed between the negative electrode plate and the positive electrode plate.
  • a microporous membrane can be used for the separator.
  • the microporous membrane is a porous sheet mainly composed of components other than fiber components. For example, after a composition containing a pore forming agent (such as polymer powder and / or oil) is extruded into a sheet, the pore forming agent is It is obtained by removing to form pores.
  • the microporous membrane is preferably made of a material having acid resistance, and is preferably composed mainly of a polymer component.
  • polyolefins such as polyethylene and a polypropylene, are preferable.
  • the electric resistance of the separator is, for example, 0.0015 ⁇ ⁇ dm 2 / sheet or more, and for example, 0.0015 to 0.0035 ⁇ ⁇ dm 2 / sheet is preferable.
  • the separator may be composed of a single microporous membrane, or a plurality of microporous membranes may be stacked.
  • the thickness (total thickness) of the separator (microporous membrane) is, for example, 0.2 to 1.5 mm.
  • the average pore diameter of the microporous membrane is, for example, 30 ⁇ m or less.
  • the electrolytic solution is an aqueous solution containing sulfuric acid, and may be gelled if necessary.
  • the specific gravity at 20 ° C. of the electrolytic solution in a fully charged lead-acid battery after formation is, for example, 1.10 to 1.35 g / cm 3 , and preferably 1.20 to 1.35 g / cm 3 .
  • the lead storage battery 1 includes a battery case 12 that accommodates an electrode plate group 11 and an electrolyte (not shown).
  • the inside of the battery case 12 is partitioned into a plurality of cell chambers 14 by a partition wall 13.
  • One electrode plate group 11 is accommodated in each cell chamber 14.
  • the opening of the battery case 12 is sealed by a lid 15 having a negative electrode terminal 16 and a positive electrode terminal 17.
  • the lid 15 is provided with a liquid plug 18 for each cell chamber. At the time of rehydration, the liquid plug 18 is removed and refilling solution is replenished.
  • the liquid plug 18 may have a function of discharging the gas generated in the cell chamber 14 out of the battery.
  • the electrode plate group 11 is configured by laminating a plurality of negative electrode plates 2 and positive electrode plates 3 with a separator 4 interposed therebetween.
  • a separator 4 which accommodates the negative electrode plate 2
  • the form of the separator is not particularly limited.
  • a porous layer (not shown) is disposed between the negative electrode plate 2 or the positive electrode plate 3 and the separator 4.
  • the negative electrode shelf 6 connecting the ears 2 a of the plurality of negative electrode plates 2 in parallel is connected to the through connection body 8, and the ears of the plurality of positive electrode plates 3
  • a positive electrode shelf 5 connecting in parallel 3 a is connected to the positive electrode post 7.
  • the positive electrode column 7 is connected to the external positive electrode terminal 17 of the lid 15.
  • the negative electrode post 9 is connected to the negative electrode shelf 6, and the through connection body 8 is connected to the positive electrode shelf 5.
  • the negative electrode post 9 is connected to the external negative electrode terminal 16 of the lid 15.
  • the through connection members 8 pass through the through holes provided in the partition walls 13 to connect the electrode plate groups 11 of the adjacent cell chambers 14 in series.
  • the lead storage battery includes a negative electrode plate, a positive electrode plate, and an electrolyte solution.
  • the negative electrode plate includes a negative electrode material containing a carbon material,
  • the carbon material includes a first carbon material having a particle size of 32 ⁇ m or more, and a second carbon material having a particle size of less than 32 ⁇ m,
  • the ratio R2 / R1 of the powder resistance R2 of the second carbon material to the powder resistance R1 of the first carbon material is 15 or more and 155 or less, It is a lead storage battery in which a porous layer is disposed between the negative electrode plate and the positive electrode plate.
  • the ratio S2 / S1 of the specific surface area S2 of the second carbon material to the specific surface area S1 of the first carbon material is preferably 20 or more.
  • the ratio S2 / S1 of the specific surface area S2 of the second carbon material to the specific surface area S1 of the first carbon material is preferably 240 or less.
  • the average aspect ratio of the first carbon material is preferably 1.5 or more.
  • the average aspect ratio of the first carbon material is preferably 30 or less.
  • the thickness of the porous layer is preferably 10 ⁇ m or more.
  • the thickness of the porous layer is preferably 500 ⁇ m or less.
  • the content of the first carbon material in the negative electrode material is preferably 0.05% by mass or more.
  • the content of the first carbon material in the negative electrode material is preferably 3.0% by mass or less.
  • the content of the second carbon material in the negative electrode material is preferably 0.03% by mass or more.
  • the content of the second carbon material in the negative electrode material is preferably 1.0% by mass or less.
  • the first carbon material contains at least graphite, and the second carbon material contains at least carbon black.
  • ⁇ Lead acid battery A1 (1) Preparation of Negative Electrode Plate
  • Lead powder, water, sulfuric acid, barium sulfate, a carbon material, an organic shrinkproofing agent, and a reinforcing material are mixed to obtain a negative electrode paste.
  • the negative electrode paste is filled in the mesh portion of the expanded lattice made of a Pb—Ca—Sn alloy, aged, and dried to obtain an unformed negative electrode plate.
  • a carbon material carbon black (average particle size D 50 : 40 nm) and graphite (average particle size D 50 : 110 ⁇ m) are used.
  • the amount of the organic anti-shrink agent added to the negative electrode paste is adjusted so that the amount of the organic anti-shrinkage agent contained in 100% by mass of the negative electrode material after formation and being fully charged is 0.2% by mass.
  • Sodium lignin sulfonate is used as the organic plasticizer.
  • the amount of barium sulfate to be added to the negative electrode paste is adjusted so that the amount of barium sulfate contained in 100% by mass of the negative electrode material after formation and being fully charged is 0.8% by mass.
  • the amount of the reinforcing material to be added to the negative electrode paste is adjusted so that the amount of the reinforcing material contained in 100% by mass of the negative electrode material after formation and being fully charged is 0.1% by mass. Synthetic fibers are used as the reinforcing material.
  • Electrode Plate Lead powder, water, sulfuric acid, and a reinforcing material are mixed to obtain a positive electrode paste.
  • the positive electrode paste is filled in the mesh portion of an expanded lattice made of a Pb—Ca—Sn alloy, aged, and dried to obtain an unformed positive electrode plate.
  • the amount of the reinforcing material to be added to the positive electrode paste is adjusted so that the amount of the reinforcing material contained in 100% by mass of the positive electrode material after formation and being fully charged is 0.1% by mass. Synthetic fibers are used as the reinforcing material.
  • a porous layer is disposed on both sides of an unformed negative electrode plate. More specifically, a non-woven fabric made of glass fiber (fiber diameter 16 ⁇ m, density 0.16 g / cm 3 , thickness 400 ⁇ m, electric resistance 0.0010 ⁇ ⁇ dm 2 ) is used for the porous layer, Stack up one by one.
  • An unformed negative electrode plate having porous layers arranged on both sides is housed in a bag-like separator formed of a microporous polyethylene membrane (average pore diameter 25 ⁇ m, thickness 0.25 mm, electrical resistance 0.0025 ⁇ ⁇ dm 2 )
  • An electrode plate group is formed of seven unformed negative electrode plates and six unformed positive electrode plates per cell.
  • the liquid lead-acid battery A1 is manufactured.
  • the nominal voltage of the lead-acid battery is 12V.
  • the nominal capacity of the lead-acid battery is 28 Ah (5 hour rate).
  • the specific gravity of the electrolytic solution poured into the battery is adjusted so that the specific gravity of the electrolytic solution after formation is 1.285.
  • the content of the first carbon material is 1.0% by mass, and the content of the second carbon material is 0.3% by mass.
  • these values are obtained when the negative electrode plate of the produced lead-acid battery is taken out and the carbon material contained in the negative electrode material is separated into the first carbon material and the second carbon material in the above-mentioned procedure. It is a value calculated
  • the powder resistance ratio R2 / R1 is 155. Powder resistance ratio R2 / R1 is calculated
  • the average aspect ratio of the first carbon material determined by the above-described procedure is 16.
  • the thickness of the porous layer (glass fiber non-woven fabric) obtained by the above-described procedure is 400 ⁇ m.
  • PSOC life test The PSOC life test is conducted in a 40 ° C. air tank under the conditions shown in Table 1. The number of cycles until the terminal voltage reaches 1.2 V per single cell is used as an indicator of PSOC life performance. It represents by the ratio when the result of the below-mentioned lead storage battery X2 is set to 100. When the PSOC life performance is 115 or more, it is evaluated that the PSOC life performance is improved.
  • this test is a test performed on the conditions which an osmotic short circuit tends to generate
  • Resistance leaving in Table 2 shows leaving lead acid battery in the state which connected 10 ohm resistance between terminals.
  • Lead-acid batteries A2 to A7 By adjusting the average particle diameter D 50 of each carbon material to be used, the specific surface area, and the average aspect ratio of the first carbon material, the powder resistance ratio R2 / R1 is set to a value shown in Table 4.
  • the specific surface area ratio S2 / S1 determined by the above-described procedure is in the range of 20 to 240.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is in the range of 1.5 to 30.
  • lead storage batteries A2 to A7 are manufactured and evaluated in the same manner as the lead storage battery A1.
  • Lead acid battery X 1 A lead storage battery X1 is prepared in the same manner as the lead storage battery A1 except that only carbon black (average particle diameter D 50 : 40 nm) is used as the carbon material and the content of the second carbon material is 0.3 mass%. And evaluate.
  • the powder resistance ratio R2 / R1 is set to a value shown in Table 2. No porous layer is disposed on both sides of the negative electrode plate.
  • the specific surface area ratio S2 / S1 determined by the above-described procedure is in the range of 20 to 240.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is in the range of 1.5 to 30.
  • lead storage batteries B1 to B5 are manufactured and evaluated in the same manner as the lead storage battery A1.
  • lead storage battery X 2 >> Only carbon black (average particle diameter D 50 : 40 nm) is used as the carbon material, and the content of the second carbon material is 0.3 mass%. No porous layer is disposed on both sides of the negative electrode plate.
  • a lead storage battery X2 is manufactured and evaluated in the same manner as the lead storage battery A1 except for the above. Table 4 shows the evaluation results of lead acid batteries A1 to A7, B1 to B5, and X1 to X2.
  • lead storage batteries B2 and B3 in which the first carbon material and the second carbon material are used as the carbon material and the powder resistance ratio R2 / R1 is 15 to 155, compared with the lead storage battery X2 using only carbon black as the carbon material Although the PSOC life performance is improved, osmotic short circuit is likely to occur. In lead acid batteries B1, B4, and B5, improvement of PSOC life performance is insufficient.
  • the reduction ratio of PSOC life performance by the arrangement of the porous layer of the lead storage battery X1 to the lead storage battery X2 is 10%.
  • the porous material is more porous than the case where only carbon black is used as the carbon material. The decrease in PSOC life performance due to the arrangement of layers is suppressed.
  • the specific surface area ratio S2 / S1 obtained in the above-described procedure is set to the value shown in Table 5.
  • the powder resistance ratio R2 / R1 obtained by the above-described procedure is set to 15 to 155.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is 1.5 to 30.
  • lead storage batteries C1 to C6 are manufactured and evaluated in the same manner as the lead storage battery A1.
  • Lead-acid batteries D1 to D5 By adjusting the specific surface area of each carbon material to be used, the specific surface area ratio S2 / S1 obtained in the above-described procedure is set to the value shown in Table 5. No porous layer is disposed on both sides of the negative electrode plate. The powder resistance ratio R2 / R1 obtained by the above-described procedure is set to 15 to 155. The average aspect ratio of the first carbon material determined by the above-described procedure is 1.5 to 30.
  • lead storage batteries D1 to D5 are manufactured and evaluated in the same manner as the lead storage battery A1. Table 5 shows the evaluation results of the lead storage batteries C1 to C6 and D1 to D5.
  • the occurrence rate of osmotic short circuit is as high as 30% or more.
  • the PSOC life performance is as high as 115 or more, and the incidence short circuit incidence rate is as low as 25% or less.
  • the lead storage batteries C1 to C4 having a specific surface area ratio S2 / S1 of 20 or more high charge acceptance performance can be obtained even when the porous layer is disposed.
  • the properties of the negative electrode paste used for producing the negative electrode plate are good, and the filling property of the negative electrode paste into the negative electrode current collector is improved. Do. Therefore, the negative electrode material is in close contact with the negative electrode current collector, and the conduction between the negative electrode material and the negative electrode current collector is good. Therefore, high PSOC life performance and charge acceptance performance can be obtained in a well-balanced manner.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is set to the value shown in Table 6.
  • the powder resistance ratio R2 / R1 obtained by the above-described procedure is set to 15 to 155.
  • the specific surface area ratio S2 / S1 obtained by the above-described procedure is set to 20 to 240.
  • lead storage batteries E1 to E5 are manufactured and evaluated in the same manner as the lead storage battery A1.
  • Lead storage batteries F1 to F4 By adjusting the average aspect ratio of the carbon material to be used, the average aspect ratio determined by the above-described procedure is set to the value shown in Table 6. No porous layer is disposed on both sides of the negative electrode plate. The powder resistance ratio R2 / R1 obtained by the above-described procedure is set to 15 to 155. The specific surface area ratio S2 / S1 obtained by the above-described procedure is set to 20 to 240. Other than the above, lead storage batteries F1 to F4 are manufactured and evaluated in the same manner as the lead storage battery A1. Table 6 shows the evaluation results of the lead storage batteries E1 to E5 and F1 to F4.
  • the occurrence rate of osmotic short circuit is as high as 30% or more.
  • PSOC life performance becomes high as 115 or more, and the occurrence of osmotic short circuit becomes low as 25% or less.
  • the lead storage batteries E2 to E4 in which the aspect ratio of the first carbon material is 1.5 to 30 high PSOC life performance is obtained, and the occurrence rate of osmotic short circuit is significantly reduced to 15% or less.
  • Lead-acid batteries G1 to G5 ⁇ By adjusting the thickness of the non-woven fabric used for the porous layer, the thickness of the porous layer obtained in the above-described procedure is made to be a value shown in Table 7.
  • the powder resistance ratio R2 / R1 determined by the above-described procedure is 15.
  • the specific surface area ratio S2 / S1 determined by the above-described procedure is 112.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is 16.
  • lead storage batteries G1 to G5 are manufactured and evaluated in the same manner as the lead storage battery A1.
  • Lead-acid battery X 3 ⁇ No porous layer is disposed on both sides of the negative electrode plate.
  • the powder resistance ratio R2 / R1 determined by the above-described procedure is 15.
  • the specific surface area ratio S2 / S1 determined by the above-described procedure is 112.
  • the average aspect ratio of the first carbon material determined by the above-described procedure is 16.
  • a lead storage battery X3 is manufactured and evaluated in the same manner as the lead storage battery A1 except for the above. Table 7 shows the evaluation results of the lead storage batteries G1 to G5 and X3.
  • the lead storage battery according to one aspect of the present invention is applicable to control valve type and liquid type lead storage batteries, and is suitable as a power supply for starting of a car or a motorbike or an industrial storage device for storage of natural energy.

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JP2006179449A (ja) * 2004-11-25 2006-07-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用電極板の製造方法
WO2012017702A1 (ja) * 2010-08-05 2012-02-09 新神戸電機株式会社 鉛蓄電池
JP2016154131A (ja) * 2015-02-18 2016-08-25 株式会社Ｇｓユアサ 鉛蓄電池
WO2017098665A1 (ja) * 2015-12-11 2017-06-15 日立化成株式会社 鉛蓄電池

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TW201136010A (en) * 2010-01-21 2011-10-16 Gs Yuasa Int Ltd Negative electrode plate using in lead storage cell, fabricating method thereof, and lead storage cell
JP6519945B2 (ja) * 2015-03-30 2019-05-29 株式会社Ｇｓユアサ 鉛蓄電池

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JP2006179449A (ja) * 2004-11-25 2006-07-06 Shin Kobe Electric Mach Co Ltd 鉛蓄電池用電極板の製造方法
WO2012017702A1 (ja) * 2010-08-05 2012-02-09 新神戸電機株式会社 鉛蓄電池
JP2016154131A (ja) * 2015-02-18 2016-08-25 株式会社Ｇｓユアサ 鉛蓄電池
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