WO2023157469A1 - アルカリ乾電池 - Google Patents

アルカリ乾電池 Download PDF

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Publication number
WO2023157469A1
WO2023157469A1 PCT/JP2022/047540 JP2022047540W WO2023157469A1 WO 2023157469 A1 WO2023157469 A1 WO 2023157469A1 JP 2022047540 W JP2022047540 W JP 2022047540W WO 2023157469 A1 WO2023157469 A1 WO 2023157469A1
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Prior art keywords
separator
negative electrode
positive electrode
mass
less
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PCT/JP2022/047540
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English (en)
French (fr)
Japanese (ja)
Inventor
潤 布目
聡 藤吉
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202280090844.2A priority Critical patent/CN118872102A/zh
Priority to JP2024500994A priority patent/JP7762860B2/ja
Priority to US18/836,340 priority patent/US20250118769A1/en
Publication of WO2023157469A1 publication Critical patent/WO2023157469A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • H01M6/085—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes of the reversed type, i.e. anode in the centre
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • 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

  • This disclosure relates to alkaline dry batteries.
  • Alkaline batteries (alkaline manganese batteries) are widely used because they have a larger capacity than manganese batteries and can draw a large amount of current. For the purpose of improving the performance of alkaline dry batteries, improvements in battery constituent members have been studied.
  • a negative electrode containing zinc powder, an electrolytic solution, a separator, and a positive electrode are provided, and the zinc powder contains 60 to 80% by weight of first zinc particles having a particle size of more than 75 ⁇ m and 425 ⁇ m or less. and 40 to 20% by weight of second zinc particles having a particle size of 75 ⁇ m or less.
  • Patent Document 2 5.0 to 45.0 g/m 2 of a crosslinked superabsorbent polymer compound having a carboxyl group is attached to a wet-laid nonwoven fabric containing alkali-resistant fibers, and alkali-resistant fibers are attached to the crosslinked base material.
  • the crosslinked superabsorbent polymer compound contains a silicate compound of 1.0 ⁇ 10 ⁇ 4 to 10 mg/cm per unit area of the separator.
  • Alkaline battery separators have been proposed which are added to contain .
  • an internal short circuit may occur during a pause during discharge.
  • An alkaline dry battery includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolytic solution contained in the positive electrode, the negative electrode, and the separator.
  • the positive electrode contains manganese dioxide
  • the half width W of the diffraction peak of the 110 plane in the X-ray diffraction pattern of the manganese dioxide is 2.4 ° or less
  • the negative electrode is a negative electrode active material containing zinc.
  • the powder is included, and the ratio of particles having a particle size of 75 ⁇ m or less to all particles in the powder is 33% by mass or more, and the thickness of the separator is 150 ⁇ m or more and 210 ⁇ m or less.
  • FIG. 1 is a partial cross-sectional front view of an alkaline dry battery according to an embodiment of the present disclosure.
  • An alkaline dry battery includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte contained in the positive electrode, the negative electrode, and the separator.
  • the positive electrode contains manganese dioxide as a positive electrode active material.
  • the negative electrode includes a negative electrode active material including zinc.
  • the electrolytes contained in the positive electrode, the negative electrode, and the separator are also referred to as "positive electrode electrolyte,” “negative electrode electrolyte,” and “separator electrolyte,” respectively.
  • the positive electrode expands and becomes more porous, and the expansion of the positive electrode compresses the separator.
  • the amount of electrolyte is reduced.
  • the pH of the electrolyte in the separator decreases.
  • the thickness of the separator is small, the amount of electrolyte in the separator tends to decrease during discharge, and the pH tends to decrease.
  • the pH of the electrolytic solution in the separator tends to decrease.
  • the pH may drop to around 9 in some cases.
  • the addition amount and molecular weight of the gelling agent also affect the ability of the negative electrode to retain the electrolyte. It is believed that the surface tension of the negative electrode active material has a greater effect.
  • the amount of the gelling agent added can affect the movement of the electrolyte solution between the negative electrode, the separator, and the positive electrode during the storage period from immediately after manufacture of the battery to the start of use.
  • the present inventors focused on the half width W and the ratio of fine particles and conducted extensive studies. As a result, it was found that when the thickness of the separator is reduced to 210 ⁇ m or less, the internal short circuit at rest during discharge can be suppressed by setting the half-value width W and the proportion of fine particles within specific ranges.
  • the alkaline dry battery according to the embodiment of the present disclosure includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte (alkaline electrolyte) contained in the positive electrode, the negative electrode, and the separator.
  • the positive electrode contains manganese dioxide, and the half width W of the diffraction peak on the 110 plane in the X-ray diffraction pattern of manganese dioxide is 2.4° or less.
  • the negative electrode contains powder of a negative electrode active material containing zinc, and particles having a particle size of 75 ⁇ m or less (hereinafter also referred to as “fine particles”) account for 33% by mass or more of all particles in the powder. .
  • the thickness T of the separator is 150 ⁇ m or more and 210 ⁇ m or less.
  • the thickness T of the separator When the half width W is 2.4° or less and the proportion of fine particles is 33% by mass or more, it is possible to increase the capacity and reduce the internal resistance by reducing the thickness T of the separator to 210 ⁇ m or less. In addition, an internal short circuit during rest during discharge is suppressed. However, if the thickness T of the separator is less than 150 ⁇ m, the distance between the positive and negative electrodes decreases and the mechanical strength of the separator decreases, and the separator may be damaged when the battery is dropped or the like, resulting in an internal short circuit. Sometimes.
  • the positive electrode contains manganese dioxide as a positive electrode active material.
  • Electrolytic manganese dioxide is usually used as the positive electrode active material, and examples of the crystal structure of electrolytic manganese dioxide include the ⁇ -type.
  • the half width W of the diffraction peak on the 110 plane in the X-ray diffraction pattern of manganese dioxide is 2.4° or less, preferably 1.8° or more and 2.4° or less, and 1.9° or more and 2.3°. ° or less is more preferable.
  • the half-value width W is 1.8° or more, the decrease in the diffusion rate of hydrogen ions in the manganese dioxide crystals and the resulting decrease in heavy-load discharge performance are suppressed.
  • the crystallite size is large, and the expansion coefficient of the crystal particles is small due to H atoms entering the crystal lattice in which Mn atoms and O atoms are arranged at predetermined sites during discharge. Therefore, expansion of the positive electrode during discharge is suppressed.
  • the above “half width W” is the full width at half maximum (FWHM).
  • the half width W is obtained by the following method.
  • the negative electrode contains zinc or a zinc alloy as a negative electrode active material.
  • the zinc alloy preferably contains at least one selected from the group consisting of indium, bismuth and aluminum.
  • the zinc alloy preferably contains 100 ppm to 280 ppm indium, 60 ppm to 200 ppm bismuth, and 10 ppm to 80 ppm aluminum.
  • the negative electrode active material is usually used in powder form. From the viewpoint of filling properties of the negative electrode and diffusibility of the alkaline electrolyte in the negative electrode, the average particle size of all particles of the negative electrode active material powder is, for example, 80 ⁇ m or more and 200 ⁇ m or less, preferably 100 ⁇ m or more and 150 ⁇ m or less. .
  • the average particle diameter means the median diameter (D50) in volume-based particle size distribution.
  • Average particle size is determined using, for example, a laser diffraction and/or scattering particle size analyzer.
  • the ratio of fine particles to all particles in the negative electrode active material powder contained in the negative electrode is 33% by mass or more, preferably 33% by mass or more and 55% by mass or less, and more preferably 36% by mass or more and 46% by mass or less. preferable.
  • the proportion of the fine particles is 55% by mass or less, the reactivity is moderately high, the rise in battery temperature during external short-circuiting is suppressed, and safety is easily ensured.
  • Fine particles are particles with a particle size of 75 ⁇ m or less, and are particles that pass through a sieve with an opening of 75 ⁇ m (200 mesh). As the ratio of fine particles to all particles in the powder of the negative electrode active material increases, the contact area between the negative electrode active material and the electrolyte increases, the discharge reaction proceeds more easily, and the electrolyte retainability of the negative electrode improves.
  • the ratio of fine particles to all particles in the negative electrode active material powder contained in the negative electrode is obtained as follows.
  • An unused (undischarged) battery is disassembled, the negative electrode is taken out, the negative electrode active material powder is taken out from the negative electrode, and its mass W0 is measured. Thereafter, fine particles (particles having a particle size of 75 ⁇ m or less) are separated from the negative electrode active material powder using a sieve, and the mass W1 thereof is measured. W1/W0 ⁇ 100 is obtained as the ratio of the fine particles.
  • the removal of the negative electrode active material powder from the negative electrode is performed as follows. First, a sufficient amount of distilled water is added to the negative electrode and stirred to wash the negative electrode active material. Specifically, the negative electrode active material is precipitated in distilled water, and the supernatant containing components other than the negative electrode active material (gelling agent, electrolytic solution, etc.) is removed. Repeat this operation several times. Further, the negative electrode active material is washed with anhydrous ethanol to remove a small amount of water adhering to the negative electrode active material, and then dried at 100° C. for a short period of time. Thereby, oxidation of the surface of the negative electrode active material can be suppressed.
  • a nonwoven fabric is preferably used as the separator.
  • a non-woven fabric sheet containing cellulose fibers and polyvinyl alcohol fibers, for example, is used for the separator.
  • a non-woven fabric sheet is obtained, for example, by blending mainly cellulose fibers and polyvinyl alcohol fibers.
  • Cellulose fibers include, for example, rayon fibers (regenerated fibers).
  • the content of polyvinyl alcohol fibers in the nonwoven fabric is, for example, 25 parts by mass or more and 150 parts by mass or less per 100 parts by mass of cellulose fibers.
  • the thickness T of the separator is 150 ⁇ m or more and 210 ⁇ m or less, preferably 170 ⁇ m or more and 200 ⁇ m or less.
  • the thickness T of the separator referred to here means the thickness of the separator in a state in which the electrolyte is absorbed in the battery, and corresponds to the distance between the positive electrode and the negative electrode in the battery.
  • a cylindrical separator is usually used as the separator placed between the positive electrode and the negative electrode.
  • the cylindrical separator may be configured by winding one base sheet having a thickness of t ( ⁇ m) into a cylindrical shape in X folds. Alternatively, it may be configured by winding a laminated sheet in which X base sheets having a thickness of t ( ⁇ m) are laminated in a single cylindrical shape.
  • the thickness t is the thickness of the base sheet in a state in which the electrolytic solution is absorbed in the battery
  • the thickness T is t ⁇ X.
  • the separator has a portion P1 where one end of the winding start of the base sheet and the other end of the winding of the base sheet overlap each other, the thickness T of the separator is the thickness of the portion other than the portion P1.
  • the thickness T of the separator is obtained as follows.
  • a cross-sectional X-ray CT image of the power generation elements (positive electrode, negative electrode, and separator containing electrolyte) contained in the battery is obtained by computed tomography (CT).
  • CT computed tomography
  • the density of the separator may be 0.22 g/cm 3 or more and 0.29 g/cm 3 or less. In this case, sufficient mechanical strength is ensured, the separator is prevented from being damaged during the manufacturing process of the battery or the battery is dropped, etc., and the positive electrode and the negative electrode can be sufficiently separated even if the thickness is small.
  • the density of the separator is obtained by dividing the mass of the separator by the volume of the separator.
  • the mass of the separator described above means the mass of the separator in a dry state without containing an electrolytic solution.
  • the mass of the separator is determined by taking out the separator from the battery, washing the separator with water to remove the electrolyte, drying the separator, and then measuring the mass.
  • the volume of the separator is obtained based on the area of the separator and the thickness T described above.
  • the area of the separator is obtained by taking out the separator from the battery and measuring the vertical and horizontal dimensions of the separator.
  • a potassium hydroxide aqueous solution for example, a potassium hydroxide aqueous solution is used.
  • the content of potassium hydroxide in the electrolytic solution is, for example, 30% by mass or more and 50% by mass or less.
  • the electrolyte may further contain zinc oxide.
  • the content of zinc oxide in the electrolytic solution is, for example, 1% by mass or more and 5% by mass or less.
  • the content (% by mass) of potassium hydroxide and zinc oxide in the electrolyte means the ratio (percentage) of the mass of potassium hydroxide and zinc oxide contained in the electrolyte to the mass of the entire electrolyte, respectively. do.
  • FIG. 1 is a front view of a horizontal half of an alkaline dry battery 10 in an embodiment of the present disclosure.
  • an alkaline dry battery 10 includes a hollow cylindrical positive electrode 2, a gelled negative electrode 3 disposed in the hollow portion of the positive electrode 2, a separator 4 disposed therebetween, and an alkaline electrolyte.
  • a power generation element including an electrolytic solution 11 that is The power generation element is housed in a bottomed cylindrical metal case 1 that also serves as a positive electrode terminal.
  • a nickel-plated steel plate is used for the case 1 .
  • the positive electrode 2 is arranged in contact with the inner wall of the case 1 .
  • the inner surface of the case 1 is preferably coated with a carbon film.
  • the bottomed cylindrical separator 4 is composed of a cylindrical separator 4a and a bottom portion 4b.
  • the separator 4a is arranged along the inner surface of the hollow portion of the positive electrode 2 to separate the positive electrode 2 and the negative electrode 3 from each other.
  • a cylindrical separator 4a is a separator arranged between the positive electrode and the negative electrode, and has a thickness of 150 ⁇ m or more and 210 ⁇ m or less.
  • the bottom portion 4b is arranged at the bottom portion of the hollow portion of the positive electrode 2 and separates the negative electrode 3 and the case 1 from each other.
  • the electrolyte 11 permeates at least the positive electrode 2, the negative electrode 3, and the separator 4. Therefore, the positive electrode electrolyte 11p and the negative electrode electrolyte 11n contained in the positive electrode 2, the negative electrode 3, and the separator 4, respectively, and the separator 11 s of internal electrolytic solutions are included at least.
  • the opening of the case 1 is sealed by a sealing unit 9.
  • the sealing unit 9 includes a resin gasket 5 , a negative terminal plate 7 that also serves as a negative terminal, and a negative current collector 6 .
  • the gasket 5 has an annular thin portion 5a that is locally thinned. When the internal pressure of the battery exceeds a predetermined value, the thin portion 5a breaks and gas is released to the outside of the battery.
  • a negative electrode current collector 6 is inserted in the negative electrode 3 .
  • the material of the negative electrode current collector 6 is, for example, an alloy containing copper and zinc, such as brass.
  • the negative electrode current collector 6 may be plated with tin, if necessary.
  • the negative electrode current collector 6 has a nail-like shape having a head portion and a body portion.
  • the head is welded to the central flat portion of the negative terminal plate 7 .
  • the open end of the case 1 is crimped to the peripheral flange of the negative electrode terminal plate 7 via the outer peripheral edge of the gasket 5 .
  • An exterior label 8 is covered on the outer surface of the case 1 .
  • the positive electrode 2 contains manganese dioxide, which is a positive electrode active material, and an electrolytic solution.
  • the half width W of the diffraction peak on the 110 plane in the X-ray diffraction pattern of manganese dioxide contained in the positive electrode 2 is 2.4° or less.
  • Manganese dioxide is used in the form of powder in the production of the positive electrode.
  • the average particle size of manganese dioxide is, for example, 25 ⁇ m or more and 55 ⁇ m or less, preferably 32 ⁇ m or more and 50 ⁇ m or less. In this case, good battery performance is likely to be obtained.
  • the particle size of manganese dioxide can be adjusted by pulverization, classification, or the like.
  • the positive electrode active material may contain other manganese oxides, oxides such as Ni, and the like.
  • the proportion of manganese dioxide in the positive electrode active material is, for example, 50% by mass or more, and may be 75% by mass or more.
  • the positive electrode 2 may contain a conductive agent in addition to manganese dioxide and an electrolytic solution.
  • conductive agents include carbon black such as acetylene black and conductive carbon materials such as graphite. Natural graphite, artificial graphite, and the like can be used as graphite.
  • the conductive agent may be fibrous or the like, but is preferably powdery.
  • the average particle size of the conductive agent can be selected, for example, from a range of 5 nm or more and 50 ⁇ m or less.
  • the average particle size of the conductive agent is preferably 5 nm or more and 40 nm or less when the conductive agent is carbon black, and preferably 3 ⁇ m or more and 50 ⁇ m or less when the conductive agent is graphite.
  • the content of graphite in the positive electrode may be 3 parts by mass or more and 8 parts by mass or less, preferably 4 parts by mass or more and 7 parts by mass or less per 100 parts by mass of manganese dioxide and graphite in total.
  • the content of graphite is 7% by mass or less, the filling amount of manganese dioxide is easily secured, and good battery performance is easily obtained.
  • the positive electrode 2 is obtained, for example, by pressing a positive electrode mixture containing a positive electrode active material, a conductive agent, and an electrolytic solution into pellets.
  • the positive electrode mixture may be made into flakes or granules, classified if necessary, and then pressure-molded into pellets. After being housed in the case, the pellet may be secondarily pressurized using a predetermined tool so as to adhere to the inner wall of the case.
  • the positive electrode (positive electrode mixture) may further contain other components (for example, polytetrafluoroethylene) as necessary.
  • the density of manganese dioxide in the positive electrode is, for example, 2.70 g/cm 3 or more and 3.10 g/cm 3 or less, preferably 2.80 g/cm 3 or more and 3.05 g/cm 3 or less.
  • the density of manganese dioxide in the positive electrode can be determined by dividing the mass of manganese dioxide contained in the positive electrode by the volume of the positive electrode.
  • the mass of manganese dioxide contained in the positive electrode is determined by removing the positive electrode from the battery, dissolving the positive electrode sufficiently with acid, removing the insoluble matter, recovering the solution, and using high-frequency inductively coupled plasma emission spectroscopy (ICP emission spectroscopy).
  • the volume of the positive electrode can be obtained by measuring the outer diameter, inner diameter, and height of the positive electrode in an X-ray CT image of the battery and based on these values.
  • the density of the positive electrode is, for example, 2.85 g/cm 3 or more and 3.30 g/cm 3 or less, preferably 2.90 g/cm 3 or more and 3.20 g/cm 3 or less.
  • the density of the positive electrode can be obtained by dividing the mass of the positive electrode by the volume of the positive electrode.
  • the mass of the positive electrode is the mass of the positive electrode including the electrolyte solution 11p in the positive electrode, and can be obtained by taking out the positive electrode from the battery and measuring the mass.
  • the volume of the positive electrode can be determined by the method described above.
  • the negative electrode 3 is in the form of a gel and contains negative electrode active material powder, an electrolytic solution, and a gelling agent.
  • the ratio of fine particles (particles having a particle diameter of 75 ⁇ m or less) to all particles in the powder of the negative electrode active material contained in the negative electrode 3 is 33% by mass or more.
  • any known gelling agent used in the field of alkaline dry batteries can be used without particular limitation, and for example, a water-absorbing polymer can be used.
  • examples of such gelling agents include polyacrylic acid and sodium polyacrylate.
  • the amount of the gelling agent added may be 0.5 parts by mass or more and 2 parts by mass or less per 100 parts by mass of the negative electrode active material.
  • the nonwoven fabric exemplified above is preferably used for the separator, and in addition to the nonwoven fabric, a microporous membrane such as cellophane may be used.
  • a cylindrical separator 4a can be used for the bottom portion 4b.
  • the bottomed cylindrical separator 4 is composed of a cylindrical separator 4a and a bottom portion 4b, but is not limited to this.
  • a bottomed cylindrical integral body may be used, and separators of known shapes used in the field of alkaline dry batteries can be used.
  • the flaky positive electrode mixture is pulverized into granules, which are classified by a 10 to 100 mesh sieve.
  • the two positive electrode pellets were placed in a battery case after pressure molding into cylindrical pellets.
  • ⁇ -type manganese dioxide powder (average particle size 40 ⁇ m) synthesized by an electrolytic method was used.
  • the values shown in Tables 1 to 3 were obtained for the half width W of the diffraction peak on the 110 plane in the powder X-ray diffraction pattern of manganese dioxide with CuK ⁇ radiation.
  • a coarse powder having a particle size of more than 75 ⁇ m and 500 ⁇ m or less and a fine powder having a particle size of 75 ⁇ m or less are obtained by using a sieve, and then the mixing ratio of the coarse powder and the fine powder is adjusted as appropriate. By doing so, the contents of fine powder in the zinc alloy powder were set to the values shown in Tables 1-3.
  • the average particle size of the zinc alloy powder was within the range of 100 ⁇ m or more and 150 ⁇ m or less.
  • a bottomed cylindrical separator 4 was placed inside the positive electrode 2 , and a predetermined amount of electrolytic solution was injected into the case 1 to be absorbed by the separator 4 .
  • the separator 4 was constructed using a cylindrical separator 4a and a bottom portion 4b.
  • a non-woven fabric sheet mainly composed of rayon fiber and polyvinyl alcohol fiber having a mass ratio of 1:1 was used.
  • the cylindrical separator 4a was constructed by winding a non-woven fabric sheet twice.
  • the thickness of the bottom portion 4b was set to 140 ⁇ m.
  • the electrolyte for impregnating the separator for pouring into the case
  • the same electrolyte as that for preparing the negative electrode was used. This state was left for a predetermined period of time to permeate the electrolytic solution from the separator 4 to the positive electrode 2 . After that, a predetermined amount of the gelled negative electrode 3 was filled inside the separator 4 .
  • the thickness T of the cylindrical separator 4a was set to the values shown in Tables 1 to 3 by changing the thickness of the nonwoven fabric sheet.
  • the filling amounts of the positive electrode 2 and the negative electrode 3 in the battery were appropriately adjusted according to the thickness T of the cylindrical separator 4a.
  • the filling amount of the positive electrode 2 was adjusted by changing the inner diameter of the positive electrode pellet.
  • the mass ratio of the positive electrode and the negative electrode filled in the battery was kept constant. The smaller the thickness T, the larger the filling amount of the positive and negative electrodes.
  • a sealing unit 9 consisting of a gasket 5 , a negative electrode terminal plate 7 and a negative electrode current collector 6 was installed in the opening of the case 1 .
  • the trunk portion of the negative electrode current collector 6 was inserted into the negative electrode 3 .
  • the open end of the case 1 was crimped onto the peripheral edge of the negative electrode terminal plate 7 via the gasket 5 to seal the opening of the case 1 .
  • the outer surface of the case 1 was covered with the outer label 8 .
  • an alkaline dry battery 10 was produced.
  • A1 to A35 are the batteries of Examples 1 to 35
  • B1 to B26 are the batteries of Comparative Examples 1 to 26.
  • the density of manganese dioxide in the positive electrode 2 was 2.93-2.96 g/cm 3 .
  • the density of the positive electrode 2 was 3.10 g/cm 3 .
  • the density of the cylindrical separator 4a was 2.7 g/m 3 .
  • the half width W is more than 2.4° and/or the ratio of fine particles to all particles in the zinc alloy powder is less than 33% by mass.
  • the alkaline dry battery according to the present disclosure is suitably used as a power source for portable audio equipment, electronic games, lights, etc., for example.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Primary Cells (AREA)
PCT/JP2022/047540 2022-02-21 2022-12-23 アルカリ乾電池 Ceased WO2023157469A1 (ja)

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US18/836,340 US20250118769A1 (en) 2022-02-21 2022-12-23 Alkaline dry cell

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008098164A (ja) * 2006-10-10 2008-04-24 Matsushita Electric Ind Co Ltd アルカリ乾電池
WO2013157181A1 (ja) * 2012-04-16 2013-10-24 パナソニック株式会社 アルカリ電池
WO2014002327A1 (ja) * 2012-06-25 2014-01-03 パナソニック株式会社 アルカリ電池
WO2020158124A1 (ja) * 2019-01-31 2020-08-06 パナソニックＩｐマネジメント株式会社 アルカリ乾電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009259706A (ja) * 2008-04-18 2009-11-05 Panasonic Corp 単３形アルカリ乾電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008098164A (ja) * 2006-10-10 2008-04-24 Matsushita Electric Ind Co Ltd アルカリ乾電池
WO2013157181A1 (ja) * 2012-04-16 2013-10-24 パナソニック株式会社 アルカリ電池
WO2014002327A1 (ja) * 2012-06-25 2014-01-03 パナソニック株式会社 アルカリ電池
WO2020158124A1 (ja) * 2019-01-31 2020-08-06 パナソニックＩｐマネジメント株式会社 アルカリ乾電池

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CN118872102A (zh) 2024-10-29

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