WO2011052118A1 - 集電体およびその製造方法、ならびにマンガン乾電池 - Google Patents

集電体およびその製造方法、ならびにマンガン乾電池 Download PDF

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Publication number
WO2011052118A1
WO2011052118A1 PCT/JP2010/005019 JP2010005019W WO2011052118A1 WO 2011052118 A1 WO2011052118 A1 WO 2011052118A1 JP 2010005019 W JP2010005019 W JP 2010005019W WO 2011052118 A1 WO2011052118 A1 WO 2011052118A1
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Prior art keywords
current collector
weight
content
mixture
binder
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PCT/JP2010/005019
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English (en)
French (fr)
Japanese (ja)
Inventor
耕司 猪口
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パナソニック株式会社
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Priority to JP2011516596A priority Critical patent/JPWO2011052118A1/ja
Priority to CN201080003014.9A priority patent/CN102197521B/zh
Priority to BRPI1005521-5A priority patent/BRPI1005521B1/pt
Publication of WO2011052118A1 publication Critical patent/WO2011052118A1/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
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/664—Ceramic materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/75—Wires, rods or strips

Definitions

  • the present invention relates to a manganese dry battery, and more particularly to an improvement of a carbon rod constituting a current collector in a manganese dry battery.
  • a hollow cylindrical positive electrode mixture is housed in a bottomed cylindrical negative electrode can.
  • a separator is disposed between the positive electrode mixture and the negative electrode can.
  • a current collector is inserted into the hollow portion of the positive electrode mixture.
  • the current collector is electrically connected to a positive terminal plate that covers the opening of the battery can.
  • the current collector generally includes (1) a step of obtaining a mixture containing a carbonaceous material and a binder, (2) a step of compressing the mixture into a rod shape to obtain a molded body, and (3) a molded body. It is manufactured through a step of firing to obtain a carbon rod and a step of (4) impregnating the carbon rod with paraffin wax.
  • Patent Document 1 proposes to heat the molded body at 100 to 350 ° C. for 3 to 20 hours in an atmosphere having an oxygen concentration of 10 to 21% before the step (3).
  • an oxidation reaction dehydrogenation reaction
  • the crosslinking of the binder proceeds.
  • the bond between the particles of the carbonaceous material is strengthened. Therefore, a dense carbon rod having high bending strength and low electrical resistance can be obtained.
  • Patent Document 2 proposes firing the compact in an atmosphere having an oxygen concentration of 0.1% or less in order to prevent oxidation of the carbon rod during firing.
  • a cylindrical tunnel furnace is used for firing the compact. While the compact is supplied into the tunnel furnace, it is continuously fired. However, it is difficult to keep the oxygen concentration uniform or constant in the furnace. In particular, the gradient of the oxygen concentration becomes significant in the longitudinal direction in the tunnel furnace. Therefore, in the proposal of Patent Document 1, the degree of oxidation of the binder, that is, the characteristics of the carbon rod is likely to vary, and the reliability is lowered. In the proposal of Patent Document 2, since the oxygen concentration in the firing furnace is low, the dehydrogenation reaction of the binder becomes insufficient.
  • an object of the present invention is to stably supply a current collector that has high bending strength, low electrical resistance, and high reliability.
  • the present invention is a current collector comprising a carbon rod and a paraffin wax impregnated in the carbon rod, wherein the carbon rod is selected from the group consisting of Fe, Cu, Ni, Co, Bi, and V It contains at least one element A, and the content of the element A in the current collector is 0.1 to 4.0% by weight.
  • the present invention also provides a hollow cylindrical positive electrode mixture containing manganese dioxide, a negative electrode can containing zinc, a separator disposed between the positive electrode mixture and the negative electrode can, and a hollow of the positive electrode mixture.
  • the present invention relates to a manganese dry battery including the above-described current collector inserted into a portion and an electrolytic solution.
  • the manufacturing method of the current collector of the present invention includes: (1) obtaining a mixture containing a carbonaceous material, a binder, and an oxidizing agent that promotes a dehydrogenation reaction of the binder; (2) compressing the mixture into a rod shape to obtain a molded body; (3) firing the molded body to obtain a carbon rod; (4) impregnating the carbon rod with paraffin wax to obtain a current collector; Including
  • the oxidizing agent includes at least one element A selected from the group consisting of Fe, Cu, Ni, Co, Bi, and V, and the content of the element A in the mixture is 0.1 to 3 .5% by weight.
  • the binder and its oxidizing agent are mixed with the carbonaceous material and fired, the dehydrogenation reaction of the binder can surely occur, and the variation in the degree of oxidation of the binder is possible. Can be reduced. Accordingly, a current collector having a high bending strength and a low electrical resistance can be obtained, and a highly reliable current collector can be obtained without variations in the characteristics of the current collector such as the bending strength and the electrical resistance.
  • the manufacturing method is (1) obtaining a mixture containing a carbonaceous material, a binder, and an oxidizing agent that promotes a dehydrogenation reaction of the binder; (2) compressing the mixture into a rod shape to obtain a molded body; (3) firing the molded body to obtain a carbon rod; (4) impregnating the carbon rod with paraffin wax to obtain a current collector; including.
  • binders such as tar and pitch contain components that promote the dehydrogenation reaction when an oxidizing agent is added.
  • the step (3) since the molded body is accommodated in a high-temperature firing furnace, it is possible to effectively promote the oxidation of the binder by the oxidant added in the step (1). That is, the dehydrogenation reaction of the binder occurs and the crosslinking proceeds. Further, when the binder contains a volatile component, the volatile component is removed. This suppresses escape of carbon atoms during firing, increases the residual carbon ratio, and strengthens the bonds between the particles of the carbonaceous material. In addition, fine voids in the carbon rod are reduced, and the bulk density is increased. Therefore, the bending strength of the current collector increases and the electrical resistance decreases.
  • the carbonaceous material is mixed with a binder and an oxidizing agent of the binder to obtain a mixture.
  • the binder and the oxidizing agent are sufficiently uniformly dispersed. Therefore, in the step (3), the binder that is uniformly dispersed in the molded body can be efficiently oxidized by the oxidizing agent that is uniformly dispersed in the molded body. Therefore, the degree of oxidation of the binder between the molded bodies and between the molded bodies can be made uniform. Further, variation in characteristics of the current collector is reduced, and a high-quality current collector with excellent reliability can be provided.
  • the oxidizing agent in step (1) includes at least one element selected from the group consisting of Fe, Cu, Ni, Co, Bi, and V (hereinafter referred to as element A).
  • element A an oxidizing agent containing element A
  • the oxidation and dehydrogenation reactions of the binder occur preferentially by the reducing action of element A at the firing temperature (about 900 to 1000 ° C.).
  • the elements A Fe and Bi are preferable. Since the oxidizing agent containing Fe is reduced during firing and exists as a sintered body of Fe after firing, the bending strength of the current collector can be increased. In addition, since Fe having excellent electron conductivity exists in the current collector, the electrical resistance of the current collector can be reduced.
  • the content of element A in the mixture of step (1) is 0.1 to 3.5% by weight.
  • the content of element A in the mixture is less than 0.1% by weight, the effect of element A is insufficient.
  • the content of element A in the mixture is more than 3.5% by weight, the elution amount of element A from the current collector increases during long-term storage of the battery, and the corrosion resistance of the negative electrode can containing zinc decreases. Storage characteristics may deteriorate.
  • the oxidizing agent containing the element A examples include an oxide containing the element A.
  • the oxide containing the element A is at least one compound selected from the group consisting of Fe 2 O 3 , Cu 2 O, NiO, Co 3 O 4 , Bi 2 O 3 , and V 2 O 5 (hereinafter referred to as compound) B) is preferred.
  • Compound B becomes a sintered body after the step (3).
  • Bi 2 O 3 and V 2 O 5 are preferable in that they also act as binders.
  • the trace amount of Fe contained as impurities also acts as the element A.
  • the amount of Fe derived from impurities contained in the current collector is about 0.05% by weight at the maximum, the effect of element A cannot be sufficiently obtained only with Fe contained as impurities in the mixture.
  • the amount of compound B added is preferably 0.1 to 3.5 parts by weight per 100 parts by weight in total of the carbonaceous material and the binder.
  • the amount of compound B added is less than 0.1 parts by weight per 100 parts by weight of the total of the carbonaceous material and the binder, the effect due to the addition of element A becomes insufficient.
  • the carbonaceous material it is preferable to use artificial graphite and at least one of carbon black and coke.
  • the coke may be coal coke or petroleum coke.
  • the ratio (W1 / W2) between the weight of artificial graphite (W1) and the weight (W2) of at least one of carbon black and coke is preferably 30/70 to 85/15.
  • the ratio (W3 / W4) of the weight of carbon black (W3) to the weight of coke (W4) (W3 / W4) is preferably 25/75 to 75/25.
  • the carbonaceous material is used as a powder.
  • the bulk specific gravity of the artificial graphite is preferably 1/3 to 1 g / ml.
  • the bulk specific gravity of coke is preferably 1/3 to 1 g / ml.
  • the bulk specific gravity of the carbon black is preferably 1/6 to 1/2 g / ml.
  • the ratio (W5 / W6) of the weight of the pitch (W5) to the weight of the tar (W6) is preferably 40/60 to 60/40.
  • Tar dry distillation liquid
  • the tar include coal tar, wood tar, and billed tar.
  • coal tar is obtained as a by-product in obtaining coke from coal.
  • Pitch is a carbonaceous solid residue obtained when tar is distilled.
  • the pitch include coal tar pitch, wood tar pitch, rosin pitch, and petroleum pitch.
  • the content of the binder in the mixture is preferably 30 to 50 parts by weight per 100 parts by weight of the carbonaceous material.
  • the content of the binder in the mixture is less than 30 parts by weight per 100 parts by weight of the carbonaceous material, the binding force between the particles of the carbonaceous material may be insufficient.
  • the content of the binder in the mixture is more than 50 parts by weight per 100 parts by weight of the carbonaceous material, the proportion of the carbonaceous material may be reduced, and the current collection characteristics may be insufficient.
  • the mixture is extruded into a rod shape to obtain a molded body.
  • the diameter of the molded body is 4.2 to 4.4 mm when the battery size is R6 (AA).
  • the compact is fired in a non-oxidizing atmosphere (for example, an inert gas atmosphere such as argon).
  • the firing temperature is, for example, 900 to 1000 ° C.
  • the firing time is, for example, 40 to 50 hours.
  • the firing furnace is preferably a tunnel furnace capable of firing the formed body continuously. Even when a tunnel furnace is used, a highly reliable current collector can be stably mass-produced.
  • step (3) since the volatile components contained in the binder are evaporated during firing, the weight of the carbon rod is reduced by about 5 to 10% by weight with respect to the weight of the molded body.
  • a cylindrical carbon rod cut to a predetermined length is impregnated with a liquid paraffin wax having a predetermined temperature (for example, a temperature higher than room temperature and higher than the melting point of paraffin wax).
  • a liquid paraffin wax having a predetermined temperature for example, a temperature higher than room temperature and higher than the melting point of paraffin wax.
  • the paraffin wax is solidified in a room temperature environment.
  • Paraffin wax is composed of, for example, a hydrocarbon compound having about 20 to 40 carbon atoms and a molecular weight of about 300 to 550.
  • 90% by weight or more of the hydrocarbon compound is normal paraffin (linear hydrocarbon compound). It is. In this way, the fine voids inside the carbon rod and the recesses on the surface of the carbon rod are filled with the paraffin wax to ensure the sealing performance of the battery.
  • the surface of the carbon rod is polished to remove paraffin wax adhering to the surface of the carbon rod, and the electron conductivity of the surface of the carbon rod is ensured.
  • a current collector is obtained.
  • the content of paraffin wax in the current collector is preferably 3 to 5 parts by weight per 100 parts by weight of carbon rods.
  • the present invention relates to a current collector obtained by the above production method. That is, the present invention is a current collector including a carbon rod and paraffin wax impregnated in the carbon rod, and the carbon rod includes an element A derived from the oxidizing agent added in the step (1). Element A is uniformly dispersed in the carbon rod. The content of element A in the current collector is 0.1 to 4.0% by weight, preferably 1.0 to 4.0% by weight.
  • the current collector of the present invention has high cohesiveness and low electrical resistance of the carbonaceous material constituting the carbon rod.
  • the current collector of the present invention can reduce the electrical resistance to 2.4 m ⁇ ⁇ cm or less, and further to 2.0 m ⁇ ⁇ cm or less, and can reduce the electrical resistance compared to the conventional current collector. Can do. Since the current collector of the present invention has a high carbon rod density, it has a high bending strength.
  • the density of the carbon rod is preferably 1.5 to 1.8 g / cm 3 .
  • the bending strength is a kind of physical property value indicating the strength against bending, and is also referred to as bending strength.
  • the amount of oxidizing agent used in the current collector manufacturing process is reduced to such an extent that the content of element A in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is sufficiently accelerated. May not be.
  • the content of element A in the current collector exceeds 4.0% by weight, the amount of element A eluted from the current collector increases during long-term storage of the battery, and the corrosion resistance of the negative electrode can containing zinc decreases. However, the storage characteristics may deteriorate.
  • the Fe content in the current collector is preferably 0.1 to 2.8% by weight.
  • the amount of oxidizing agent used in the current collector manufacturing process is reduced to such an extent that the Fe content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than Fe is included.
  • the Fe content in the current collector is particularly preferably 0.7 to 2.8% by weight. Since the electric resistance can be reduced to 1.6 m ⁇ ⁇ cm or less and the strong discharge characteristics can be greatly improved, the Fe content in the current collector is further preferably 1.0 to 2.8% by weight.
  • the Bi content in the current collector is preferably 0.1 to 3.6% by weight.
  • the amount of oxidizing agent used in the current collector manufacturing process is reduced to such an extent that the Bi content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than Bi is included.
  • the Bi content in the current collector exceeds 3.6% by weight, the electrical resistance and bending strength of the current collector are almost the same as in the case of 3.6% by weight. Since the electrical resistance can be reduced to 2.0 m ⁇ ⁇ cm or less and the bending strength can be increased to 50 MPa or more, the Bi content in the current collector is more preferably 0.5 to 3.6% by weight.
  • the Bi content in the current collector is particularly preferably 1.0 to 3.6% by weight. Since the electric resistance can be reduced to 1.7 m ⁇ ⁇ cm or less and the strong discharge characteristics can be greatly improved, the Bi content in the current collector is preferably 1.5 to 3.6% by weight.
  • the V content of the current collector is preferably 0.1 to 2.5% by weight.
  • the amount of oxidizing agent used in the current collector manufacturing process is reduced to such an extent that the V content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than V is included.
  • the Cu content of the current collector is preferably 0.1 to 3.4% by weight.
  • the amount of the oxidizing agent used in the current collector production process is reduced to such an extent that the Cu content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than Cu is included.
  • the Ni content of the current collector is preferably 0.1 to 3.2% by weight.
  • the amount of the oxidizing agent used in the current collector manufacturing process is reduced to such an extent that the Ni content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than Ni is included.
  • the Ni content in the current collector exceeds 3.2% by weight, the electrical resistance and bending strength of the current collector are almost the same as in the case of 3.2% by weight. Since the electric resistance can be reduced to 2.0 m ⁇ ⁇ cm or less, the Ni content in the current collector is more preferably 0.5 to 3.2 wt%. Since the electric resistance can be reduced to 1.7 m ⁇ ⁇ cm or less and the strong discharge characteristics can be greatly improved, the Ni content in the current collector is further preferably 1.0 to 3.2 wt%.
  • the Co content of the current collector is preferably 0.1 to 3.0% by weight.
  • the amount of oxidizing agent used in the current collector production process is reduced to such an extent that the Co content in the current collector is less than 0.1% by weight, the dehydrogenation reaction of the binder is not sufficiently promoted. There is. However, this is not the case when an element A other than Co is included.
  • FIG. 1 is a front view of a cross section of a part of an AA manganese dry battery (R6).
  • a hollow cylindrical positive electrode mixture 1 is accommodated in a bottomed cylindrical negative electrode can 4 containing zinc.
  • a separator 3 is disposed between the positive electrode mixture 1 and the negative electrode can 4.
  • the separator 3 for example, kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of polyvinyl acetate in an alcohol solvent and dried is used.
  • the separator 3 is arranged so that the surface on which the paste material is applied faces the negative electrode can 4.
  • the separator 3 contains an electrolytic solution.
  • the electrolytic solution for example, an aqueous solution containing zinc chloride is used.
  • a positive electrode current collector 2 is inserted into the hollow portion of the positive electrode mixture 1.
  • the positive electrode mixture for example, a powdery conductive agent such as powdered manganese dioxide or acetylene black, and a mixture of an electrolytic solution are used.
  • the content of manganese dioxide in the positive electrode mixture 1 is preferably 40 to 60% by weight.
  • the content of the conductive agent in the positive electrode mixture 1 is preferably 5 to 15% by weight.
  • the cylindrical positive electrode current collector 2 is inserted into the hole in the center of the resin gasket 5.
  • a sealing agent such as polybutene is applied.
  • a circular paper 9 having a through-hole in the center is disposed on the positive electrode mixture 1, and the positive electrode current collector 2 is inserted into the through-hole of the paper 9.
  • the opening of the negative electrode can 4 is covered with a gasket 5 and a positive electrode terminal 11 made of a cap-shaped tin plate having a convex portion at the center and a flat plate-like collar portion around it.
  • the top part of the positive electrode current collector 2 is fitted into a concave part formed inside the convex part of the positive electrode terminal 11 and is electrically connected.
  • a resin-made insulating ring 12 is disposed on the flat collar portion of the positive electrode terminal 11.
  • a bottom paper 13 is provided between them.
  • a seal ring 7 is disposed on the outer surface side of the flat plate-like outer peripheral portion of the negative electrode terminal 6.
  • a resin tube 8 made of a heat-shrinkable resin film is disposed on the outer periphery of the negative electrode can 4.
  • the upper end portion of the resin tube 8 covers the upper surface of the outer peripheral portion of the gasket 5, and the lower end portion of the resin tube 8 is the seal ring 7. Cover the lower surface of.
  • a metal outer can 10 made of a cylindrical tin plate is disposed outside the resin tube 8, and a lower end portion thereof is bent inward so as to cover the seal ring 7.
  • the manganese dry battery is hermetically sealed by curling the upper end portion of the metal outer can 10 inward and caulking the tip of the upper end portion to the positive electrode terminal 11 via the insulating ring 12.
  • the current collector of the present invention is used for the positive electrode current collector 2. Since the current collector of the present invention has a low electric resistance, a battery having a low internal resistance can be obtained. Since the current collector of the present invention has a high bending strength, when the battery is assembled (for example, when the current collector is inserted into the hollow portion of the positive electrode mixture and the hole of the gasket, and the current collector is inserted into the concave portion of the positive electrode terminal. The occurrence of cracks and breakage of the current collector due to an excessive force applied to the current collector during fitting) is suppressed. The leakage of the electrolyte from the fitting portion between the top of the current collector and the positive electrode terminal due to the presence of cracks at the top of the current collector is suppressed. Therefore, the reliability of the battery is improved.
  • powdered Fe 2 O 3 (manufactured by Kanto Chemical Co., Inc., deer special grade, average particle size of 3 ⁇ m) is added to the total of 100 parts by weight of the carbonaceous material and the binder, and the mixture is mixed. Got. This mixture was kneaded for 90 minutes with a Z-type stirrer.
  • Table 2 shows the Fe content in the mixture.
  • Fe in the mixture of the comparative example 1 of Table 2 is Fe contained as an impurity in the material of Table 1.
  • Fe in the mixtures of Examples 1 to 6 in Table 2 is the sum of Fe contained as impurities in the materials in Table 1 and Fe in the oxidizing agent.
  • the mixture was molded by an extrusion molding machine to obtain a cylindrical molded body (diameter 4 mm, length 700 mm).
  • the formed body was fired in a tunnel furnace to obtain a carbon rod.
  • the atmosphere was a non-oxidizing atmosphere, the firing temperature was 1000 ° C., and the firing time was 48 hours.
  • the binder caused a dehydrogenation reaction by the oxidizing agent, and the crosslinking of the binder proceeded. Since the volatile components evaporated from the molded body during firing, the weight of the carbon rod was about 90% of the weight of the molded body.
  • the volatile component is a low molecular weight component contained in tar or pitch.
  • the density of the carbon rod was 1.72 g / cm 3 .
  • the carbon rod was cut to a length of 50 mm.
  • the carbon rod was immersed in 120 ° C. liquid paraffin wax (manufactured by Taiwan Wax Company, white wax) for 2 hours.
  • the paraffin wax contained in the carbon rod was solidified at room temperature.
  • the surface of the carbon rod containing paraffin wax was polished to obtain a cylindrical current collector (diameter 4 mm, length 47.2 mm).
  • the paraffin content in the current collector was about 5 parts by weight per 100 parts by weight of the carbon rod.
  • Table 3 shows the Fe content in the current collector.
  • the current collector was arranged so that the longitudinal direction of the current collector was horizontally oriented, and the current collector was supported by a pair of fulcrums.
  • the pair of fulcrums were symmetrically arranged at a predetermined distance L from each other along the longitudinal direction of the current collector.
  • a load was applied from the opposite side (upper side) of the pair of fulcrums to determine a load W at which the current collector was broken.
  • the bending strength F was obtained from the following formula (2).
  • the distance L was 30 mm.
  • F (8L / ⁇ D 3 ) ⁇ W (2)
  • the current collectors of Examples 1 to 6 showed lower electrical resistance and greater bending strength than the current collector of Comparative Example 1.
  • Examples 7 to 10 Powdered Bi 2 O 3 (manufactured by Kanto Chemical Co., Ltd., deer grade) was added to 100 parts by weight of the total of the carbonaceous material and the binder at a ratio shown in Table 4 to obtain a mixture.
  • Table 4 shows the Fe content in the mixture.
  • Fe in the mixture of Table 4 is Fe contained as an impurity in the material of Table 1.
  • a current collector was produced in the same manner as in Example 1 using the above mixture.
  • Table 5 shows the Bi content and the Fe content in the current collector.
  • the current collectors of Examples 7 to 10 were evaluated by the same method as described above. The results are shown in Table 5. The current collectors of Examples 7 to 10 exhibited lower electrical resistance and greater bending strength than the current collector of Comparative Example 1.
  • Examples 11 to 14 Powdered V 2 O 5 (manufactured by Kanto Chemical Co., Ltd., special grade) was added at a ratio shown in Table 6 to a total of 100 parts by weight of the carbonaceous material and the binder to obtain a mixture.
  • Table 6 shows the Fe content in the mixture.
  • Fe in the mixture of Table 6 is Fe contained as an impurity in the material of Table 1.
  • a current collector was produced in the same manner as in Example 1 using the above mixture.
  • Table 7 shows the V content and the Fe content in the current collector.
  • the current collectors of Examples 11 to 14 were evaluated by the same method as described above. The results are shown in Table 7. The current collectors of Examples 11 to 14 exhibited lower electrical resistance and greater bending strength than the current collector of Comparative Example 1.
  • Examples 15 to 18 Powdered Cu 2 O (manufactured by Kanto Chemical Co., Ltd., deer special grade) was added to the total of 100 parts by weight of the carbonaceous material and the binder at a ratio shown in Table 8 to obtain a mixture.
  • Table 8 shows the Fe content in the mixture.
  • Fe in the mixture of Table 8 is Fe contained as an impurity in the material of Table 1.
  • a current collector was produced in the same manner as in Example 1 using the above mixture.
  • Table 9 shows the Cu content and the Fe content in the current collector.
  • the current collectors of Examples 15 to 18 were evaluated by the same method as described above. The results are shown in Table 9. The current collectors of Examples 15 to 18 exhibited lower electrical resistance and larger bending strength than the current collector of Comparative Example 1.
  • Examples 19 to 22 Powdered NiO (manufactured by Kanto Chemical Co., Inc., deer special grade) was added to 100 parts by weight of the total of the carbonaceous material and the binder to obtain a mixture.
  • Table 10 shows the Fe content in the mixture.
  • Fe in the mixture of Table 10 is Fe contained as an impurity in the material of Table 1.
  • a current collector was produced in the same manner as in Example 1 using the above mixture.
  • Table 11 shows the Ni content and the Fe content in the current collector.
  • the current collectors of Examples 19 to 22 were evaluated by the same method as described above. The results are shown in Table 11. The current collectors of Examples 19 to 22 exhibited lower electrical resistance and greater bending strength than the current collector of Comparative Example 1.
  • Examples 23 to 26 >> Powdered Co 3 O 4 (manufactured by Kanto Chemical Co., Inc.) was added at a ratio shown in Table 12 to 100 parts by weight of the total of the carbonaceous material and the binder to obtain a mixture.
  • Table 12 shows the Fe content in the mixture.
  • Fe in the mixture of Table 12 is Fe contained as an impurity in the material of Table 1.
  • a current collector was produced in the same manner as in Example 1 using the above mixture.
  • Table 13 shows the V content and the Fe content in the current collector.
  • the current collectors of Examples 23 to 26 were evaluated by the same method as described above. The results are shown in Table 13. The current collectors of Examples 23 to 26 exhibited lower electrical resistance and greater bending strength than the current collector of Comparative Example 1.
  • the AA manganese dry battery (R6) of the present invention shown in FIG. 1 was produced by the following procedure.
  • a cylindrical positive electrode mixture 1 was housed in a bottomed cylindrical negative electrode can 4 made of a zinc alloy containing 0.4% by weight of lead.
  • the separator 3 was disposed between the positive electrode mixture 1 and the negative electrode can 4.
  • a kraft paper coated with a paste obtained by dissolving a cross-linked starch and a binder mainly composed of polyvinyl acetate in an alcohol solvent and dried was used. Then, the separator 3 was disposed so that the surface on which the paste material was applied was opposed to the negative electrode can 4. Next, a circular paper 9 having an opening was placed on top of the positive electrode mixture 1.
  • the current collector 2 was disposed in the hollow portion of the positive electrode mixture 1.
  • the positive electrode mixture a mixture of manganese dioxide, acetylene black, and an electrolytic solution in a weight ratio of 45:10:45 was used.
  • An aqueous solution containing 30% by weight of zinc chloride was used as the electrolytic solution.
  • a gasket 5 made of a polyolefin resin and having a hole in the center was prepared.
  • the positive electrode current collector 2 was fitted into the hole at the center.
  • polybutene was interposed as a sealant in the fitting portion between the gasket 5 and the positive electrode current collector 2.
  • a positive electrode terminal 11 made of a cap-shaped tin plate having a convex portion at the center and a flat collar portion around the convex portion was prepared.
  • the upper part of the positive electrode current collector 2 was fitted into a concave portion at the center of the positive electrode terminal 11, and a resin insulating ring 12 was disposed on the flat plate-like collar portion of the positive electrode terminal 11.
  • a bottom paper 13 was provided between the bottom of the positive electrode mixture 1 and the negative electrode can 4 to ensure insulation between them.
  • a seal ring 7 was disposed on the outer surface side of the flat plate-like outer peripheral portion of the negative electrode terminal 6.
  • a resin tube 8 made of a heat-shrinkable resin film is provided on the outer periphery of the negative electrode can 4, and its upper end covers the upper surface of the outer periphery of the gasket 5 and its lower end is a seal ring. Heat shrinkage was performed so as to cover the lower surface of 7.
  • a metal outer can 10 made of a cylindrical tin plate is placed outside the resin tube 8, its lower end is bent inward, its upper end is curled inward, and the tip of its upper end is insulated ring 12. Squeezed.
  • the current collectors of Examples 1 to 26 and Comparative Example 1 were used to produce the batteries A1 to A26 of Examples 1 to 26 and the battery B1 of Comparative Example 1, respectively.
  • a step of discharging at 1.8 ⁇ for 15 seconds and then resting for 45 seconds was repeated until the discharge voltage reached 0.9V.
  • the number of repetitions (number of cycles) at this time was determined. The results are shown in Tables 14-18.
  • the batteries A1 to A10 of Examples 1 to 10 showed a larger cycle number than the battery B1 of Comparative Example 1.
  • the number of cycles was about 180 cycles or more, and excellent strong discharge characteristics were obtained.
  • the number of cycles was about 190 cycles, and the strong discharge characteristics were greatly improved.
  • the batteries A11 to A26 of Examples 11 to 26 showed a larger cycle number than the battery B1 of Comparative Example 1.
  • batteries A12 to A14, A16 to A18, A20 to A22, and A24 to A26 had an excellent cycle number of about 180 cycles or more. Strong discharge characteristics were obtained.
  • the number of cycles was about 190 cycles or more, and the strong discharge characteristics were Greatly improved.
  • the battery A18 of Example 18 exhibited the most excellent strong discharge characteristics.
  • the manganese dry battery of the present invention is suitably used as a power source for electronic devices such as portable devices.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
PCT/JP2010/005019 2009-10-26 2010-08-10 集電体およびその製造方法、ならびにマンガン乾電池 WO2011052118A1 (ja)

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JP2011516596A JPWO2011052118A1 (ja) 2009-10-26 2010-08-10 集電体およびその製造方法、ならびにマンガン乾電池
CN201080003014.9A CN102197521B (zh) 2009-10-26 2010-08-10 集流体及其制造方法、以及锰干电池
BRPI1005521-5A BRPI1005521B1 (pt) 2009-10-26 2010-08-10 Coletor de corrente, bateria seca de manganês, e, método para produzir um coletor de corrente

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CN111864224B (zh) * 2019-11-26 2021-10-15 宁波丰银电池有限公司 一种锌锰干电池制造工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57202662A (en) * 1981-06-08 1982-12-11 Hitachi Maxell Ltd Carbon rod for dry cell
JPS57202661A (en) * 1981-06-08 1982-12-11 Hitachi Maxell Ltd Carbon rod for dry cell
JPH042056A (ja) * 1990-04-17 1992-01-07 Matsushita Electric Ind Co Ltd 乾電池用炭素棒の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5460B2 (zh) * 1973-12-20 1979-01-05
JP2005026151A (ja) * 2003-07-04 2005-01-27 Matsushita Electric Ind Co Ltd マンガン乾電池用正極集電体およびそれを用いたマンガン乾電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57202662A (en) * 1981-06-08 1982-12-11 Hitachi Maxell Ltd Carbon rod for dry cell
JPS57202661A (en) * 1981-06-08 1982-12-11 Hitachi Maxell Ltd Carbon rod for dry cell
JPH042056A (ja) * 1990-04-17 1992-01-07 Matsushita Electric Ind Co Ltd 乾電池用炭素棒の製造方法

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CR20110242A (es) 2011-10-10
BRPI1005521A2 (pt) 2016-02-23

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