WO2025028348A1 - リチウム一次電池 - Google Patents

リチウム一次電池 Download PDF

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WO2025028348A1
WO2025028348A1 PCT/JP2024/026343 JP2024026343W WO2025028348A1 WO 2025028348 A1 WO2025028348 A1 WO 2025028348A1 JP 2024026343 W JP2024026343 W JP 2024026343W WO 2025028348 A1 WO2025028348 A1 WO 2025028348A1
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positive electrode
mass
metal
lithium
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French (fr)
Japanese (ja)
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弘平 齋藤
正信 竹内
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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 CN202480049345.8A priority Critical patent/CN121586944A/zh
Priority to JP2025537342A priority patent/JPWO2025028348A1/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
    • H01M4/06—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
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte

Definitions

  • This disclosure relates to lithium primary batteries.
  • Lithium primary batteries have a high energy density and low self-discharge, and are therefore used as the power source for many electronic devices.
  • Manganese dioxide and the like are used for the positive electrode of a lithium primary battery.
  • sheet-shaped (foil-shaped) lithium metal or lithium alloy is used for the negative electrode of a lithium primary battery.
  • Patent Document 1 proposes a lithium negative electrode in which "in a lithium-organic electrolyte battery in which a lithium salt is dissolved in the electrolyte and a separator faces the negative electrode, an aluminum-magnesium alloy coating layer is initially laminated on the surface of the lithium body adjacent to the separator, and the negative electrode is formed with an aluminum-magnesium-lithium ternary alloy by diffusion, increasing the surface area of the negative electrode and improving the pulse performance of the battery.”
  • Patent document 2 proposes a battery that "includes a negative electrode that uses a light metal as an active material, an organic electrolyte, and a positive electrode that uses manganese dioxide as an active material, the positive electrode being characterized in that it is made of a mixture of alkaline earth metal oxides.”
  • Patent Document 3 proposes a "positive electrode for a lithium primary battery, characterized in that at least one metal oxide selected from the group consisting of titanium oxide, alumina, zinc oxide, chromium oxide, lithium oxide, nickel oxide, copper oxide, and iron oxide is dispersed between manganese dioxide particles.”
  • the internal resistance can increase after long-term storage, causing a decrease in discharge characteristics.
  • a lithium primary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte
  • the positive electrode including a positive electrode mixture, the positive electrode mixture including manganese dioxide and an oxide of a metal Me other than manganese, the metal Me having a valence of 2 or more, an ionic radius of 0.8 ⁇ or less, and an electronegativity of 1.65 or less, the amount of the oxide of the metal Me included in the positive electrode mixture being 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the manganese dioxide included in the positive electrode mixture, the negative electrode including an alloy including lithium and magnesium, the content of the lithium in the alloy being more than 88% by mass, and the content of the magnesium in the alloy being 0.01% by mass or more and 10% by mass or less.
  • FIG. 1 is a partially cross-sectional front view of a lithium primary battery according to an embodiment of the present disclosure.
  • the lithium primary battery according to the embodiment of the present disclosure includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • the positive electrode includes a positive electrode mixture, which includes manganese dioxide (positive electrode active material) and an oxide of a metal Me other than manganese (additive).
  • the metal Me has a valence of 2 or more, an ionic radius of 0.8 ⁇ (angstroms) or less, and an electronegativity of 1.65 or less.
  • the amount of the oxide of the metal Me included in the positive electrode mixture is 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of manganese dioxide included in the positive electrode mixture.
  • the negative electrode includes an alloy including lithium (Li) and magnesium (Mg).
  • the alloy is also referred to as a "lithium alloy including Mg".
  • the Li content in the lithium alloy is more than 88% by mass.
  • the Mg content in the lithium alloy is 0.01% by mass or more and 10% by mass or less
  • the deterioration of the non-aqueous electrolyte during storage is suppressed, and the gas generation and increase in internal resistance associated with the decomposition of the solvent are suppressed, and the deterioration of storage characteristics is suppressed to a certain extent.
  • the decomposition of the solvent involves hydroxyl groups present on the surface of manganese dioxide and trace amounts of water that are inevitably included in the non-aqueous electrolyte during production.
  • the storage characteristics are still insufficient, and the inventors have conducted extensive research to improve the storage characteristics. As a result, it has been newly discovered that the deterioration of storage characteristics is significantly suppressed by including an oxide of metal Me in the positive electrode mixture and including Mg in the lithium alloy of the negative electrode.
  • the increase in internal resistance after long-term storage and the associated decrease in discharge characteristics are suppressed.
  • the decrease in storage characteristics is suppressed.
  • the detailed mechanism is unknown, but it is speculated as follows.
  • the metal Me contained in the positive electrode mixture dissolves from the positive electrode and precipitates on the negative electrode, and the metal Me is incorporated into the coating formed on the negative electrode surface by contact between the negative electrode and the non-aqueous electrolyte.
  • the dispersibility of the metal Me in the coating is low, Li ions are less likely to move within the coating, and the negative electrode resistance may increase.
  • the amount of the oxide of the metal Me contained in the positive electrode mixture is less than 0.1 parts by mass per 100 parts by mass of manganese dioxide contained in the positive electrode mixture, the effect of adding the oxide of the metal Me will be small, and the suppression of deterioration of storage characteristics will be insufficient. If the amount of the oxide of the metal Me contained in the positive electrode mixture is greater than 5 parts by mass per 100 parts by mass of manganese dioxide contained in the positive electrode mixture, the proportion of the oxide of the metal Me in the positive electrode mixture will be large, leading to an increase in the positive electrode resistance and a deterioration in discharge characteristics.
  • the proportion of Mg in the negative electrode increases, which may increase the negative electrode resistance and deteriorate the discharge characteristics. If the Li content in the lithium alloy is 88 mass % or less, the proportion of Li in the negative electrode decreases, which may increase the negative electrode resistance and deteriorate the discharge characteristics.
  • the metal Me has a valence of 2 or more, an ionic radius of 0.8 ⁇ or less, and an electronegativity of 1.65 or less.
  • the valence of the metal Me is within the above range, the Li ion conductivity in the coating is improved due to the presence of the metal Me in the coating, which has a valence greater than that of Li.
  • the ionic radius and electronegativity of the metal Me are within the above range, the movement of lithium ions in the coating is less likely to be hindered due to factors such as a small difference from the ionic radius and electronegativity of Li.
  • the valence of metal Me is the valence when metal Me exists as an oxide of metal Me.
  • the ionic radius and electronegativity of metal Me are Pauling ionic radius and electronegativity.
  • Metal Me may be used alone or in combination of two or more kinds.
  • the metal Me preferably contains at least one selected from the group consisting of magnesium (Mg), aluminum (Al), titanium (Ti), zinc (Zn), zirconium (Zr), and niobium (Nb).
  • magnesium (Mg) is particularly preferred as the metal Me from the viewpoint of high surface coverage of manganese dioxide.
  • the oxide of the metal Me preferably includes at least one selected from the group consisting of MgO, Al 2 O 3 , TiO 2 , ZnO, ZrO 2 , and Nb 2 O 5.
  • the positive electrode mixture includes, for example, positive electrode active material particles, an oxide of the metal Me, and a binder.
  • the positive electrode mixture may include a composite in which the surface of the positive electrode active material particles is coated with an oxide of the metal Me. In order to obtain the composite, a composite treatment may be performed using the positive electrode active material particles and the oxide particles of the metal Me.
  • the positive electrode mixture may also include a mixture of the positive electrode active material particles and the oxide particles of the metal Me.
  • the oxide of the metal Me may be used alone or in combination of two or more.
  • the amount of metal Me oxide contained in the positive electrode mixture is 0.1 parts by mass or more and 5 parts by mass or less, and preferably 0.5 parts by mass or more and 2 parts by mass or less, per 100 parts by mass of manganese dioxide contained in the positive electrode mixture.
  • the amount of Mg atoms contained in the positive electrode mixture is preferably 0.1 parts by mass or more and 4.8 parts by mass or less, and more preferably 0.48 parts by mass or more and 1.9 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • the amount of Al atoms contained in the positive electrode mixture is preferably 0.08 parts by mass or more and 4.2 parts by mass or less, and more preferably 0.42 parts by mass or more and 1.7 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • the amount of Ti atoms contained in the positive electrode mixture is preferably 0.095 parts by mass or more and 4.7 parts by mass or less, and more preferably 0.47 parts by mass or more and 1.9 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • the positive electrode mixture contains ZnO and manganese dioxide
  • the amount of Zn atoms contained in the positive electrode mixture is preferably 0.13 parts by mass or more and 6.4 parts by mass or less, and more preferably 0.64 parts by mass or more and 2.5 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • the amount of Zr atoms contained in the positive electrode mixture is preferably 0.12 parts by mass or more and 5.9 parts by mass or less, and more preferably 0.59 parts by mass or more and 2.3 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • the positive electrode mixture contains Nb2O5 and manganese dioxide
  • the amount of Nb atoms contained in the positive electrode mixture is preferably 0.11 parts by mass or more and 5.5 parts by mass or less, and more preferably 0.55 parts by mass or more and 2.2 parts by mass or less, per 100 parts by mass of Mn atoms contained in the positive electrode mixture.
  • Mg , Al, Ti, Zn, Zr, and Nb are respectively derived from MgO, Al2O3 , TiO2 , ZnO, ZrO2 , and Nb2O5 .
  • Mn is derived from manganese dioxide.
  • the amount (parts by mass) of metal Me atoms contained in the above positive electrode mixture can be determined as follows. An initial battery (e.g., an unused battery immediately after manufacture or within one week after purchase) is disassembled to remove the positive electrode mixture, which is then dissolved in an acid solution (hydrochloric acid, etc.), and the insoluble matter is separated by filtration or centrifugation to obtain a sample solution. The amount of metal Me WMe (mass%) and the amount of Mn WMn (mass%) in the sample solution are measured by inductively coupled plasma (ICP) emission spectroscopy, and (WMe/WMn) x 100 is calculated as the amount (parts by mass) of the metal Me atoms. For example, Thermo Fisher Scientific's "iCAP7400 Duo" can be used as the measurement device.
  • ICP inductively coupled plasma
  • the Li content in the lithium alloy is more than 88% by mass, and may be 89% by mass or more, 90% by mass or more, or 95% by mass or more.
  • the Li content in the lithium alloy may be 99.99% by mass or less.
  • the Mg content in the lithium alloy is 0.01% by mass or more and 10% by mass or less.
  • the lithium alloy further contains Al.
  • a lithium alloy that contains Mg and substantially no Al is also referred to as a "Li-Mg alloy.”
  • a lithium alloy that contains Mg and Al is also referred to as a "Li-Mg-Al alloy.”
  • substantially no means that the content is below the detection limit in a composition analysis of the lithium alloy (e.g., ICP atomic emission spectrometry, atomic absorption spectrometry, etc.).
  • Mg has very good dispersibility in Li.
  • a lithium alloy contains both Mg and Al
  • the good dispersibility of Mg suppresses the segregation of Al, and uneven Li consumption due to Al segregation is suppressed.
  • the effects of Mg and Al are stably obtained throughout the negative electrode, Li is consumed uniformly on the negative electrode surface, and the proportion of Li that can contribute to the discharge reaction at the end of discharge becomes larger.
  • Al is included together with Mg, a low-resistance coating is easily formed stably, the voltage at the end of discharge is further increased, and the deterioration of storage characteristics is further suppressed.
  • the Mg content in the lithium alloy is 0.01 mass% or more, preferably 0.2 mass% or more, and more preferably 0.5 mass% or more. From the viewpoint of reducing the negative electrode resistance, the Mg content in the lithium alloy is 10 mass% or less, preferably 5 mass% or less, and more preferably 2 mass% or less. The range of the Mg content in the lithium alloy may be, for example, 0.2 mass% or more and 5 mass% or less, or 0.5 mass% or more and 2 mass% or less.
  • the Mg content in the lithium alloy is the Mg content in a Li-Mg alloy or a Li-Mg-Al alloy.
  • the Al content in the lithium alloy is preferably 0.01 mass% or more (or 0.1 mass% or more) and 5 mass% or less, and more preferably 0.1 mass% or more and 4 mass% or less (or 3 mass% or less).
  • the total content of Mg and Al in the Li-Mg-Al alloy is preferably 0.02 mass% or more and 10 mass% or less.
  • the molar ratio of Mg to Al: Mg/Al may be, for example, in the range of 0.02 mass% or more and 3 mass% or less.
  • the lithium alloy may contain other metal elements in addition to Li, Mg, and Al.
  • other metal elements include Sn, Ni, Pb, In, Na, K, and Ca.
  • the composition of the lithium alloy can be determined by inductively coupled plasma (ICP) optical emission spectrometry or atomic absorption spectrometry (AAS).
  • ICP inductively coupled plasma
  • AAS atomic absorption spectrometry
  • the lithium primary battery disclosed herein is described in more detail below.
  • the positive electrode includes a positive electrode mixture.
  • the positive electrode mixture includes manganese dioxide as a positive electrode active material.
  • a positive electrode including manganese dioxide exhibits a relatively high voltage and has excellent pulse discharge characteristics.
  • the manganese dioxide one obtained by calcining electrolytic manganese dioxide is preferably used.
  • the manganese dioxide may be in a mixed crystal state including a plurality of crystal states.
  • the positive electrode may include a manganese oxide other than manganese dioxide. Examples of the manganese oxide other than manganese dioxide include MnO, Mn3O4 , Mn2O3 , and Mn2O7 . It is preferable that the main component of the manganese oxide included in the positive electrode is manganese dioxide.
  • the manganese dioxide contained in the positive electrode may be doped with a small amount of lithium. If the amount of lithium doped is small, a high capacity can be ensured.
  • Manganese dioxide and manganese dioxide doped with a small amount of lithium can be expressed as Li x MnO 2 (0 ⁇ x ⁇ 0.05).
  • the average composition of the entire manganese oxide contained in the positive electrode may be Li x MnO 2 (0 ⁇ x ⁇ 0.05).
  • the ratio x of Li may be 0.05 or less in the initial state of discharge of the lithium primary battery. The ratio x of Li generally increases with the progress of discharge of the lithium primary battery. Theoretically, the oxidation number of manganese contained in manganese dioxide is tetravalent.
  • the oxidation number of manganese may increase or decrease slightly from tetravalent. Therefore, in Li x MnO 2 , the average oxidation number of manganese is allowed to increase or decrease slightly from tetravalent.
  • the positive electrode may contain, in addition to manganese dioxide, other positive electrode active materials used in lithium primary batteries.
  • other positive electrode active materials include graphite fluoride.
  • the proportion of manganese dioxide in the total positive electrode active material is preferably 90 mass% or more.
  • electrolytic manganese dioxide is preferably used. By adjusting the conditions during firing, the crystallinity of the manganese dioxide can be increased and the specific surface area of the electrolytic manganese dioxide can be reduced.
  • the BET specific surface area of the manganese dioxide may be 5 m 2 /g or more and 40 m 2 /g or less. When the BET specific surface area of the manganese dioxide is within the above range, self-discharge is suppressed and the deterioration of the pulse discharge characteristics after storage can be further suppressed.
  • the BET specific surface area of manganese dioxide may be measured by a known method, for example, using a specific surface area measuring device (for example, manufactured by Mountec Co., Ltd.) based on the BET method.
  • a specific surface area measuring device for example, manufactured by Mountec Co., Ltd.
  • manganese dioxide separated from the positive electrode removed from a battery may be used as the measurement sample.
  • the median particle size of manganese dioxide may be 5 ⁇ m or more and 40 ⁇ m or less. When the median particle size is within the above range, self-discharge is suppressed, and the deterioration of pulse discharge characteristics after storage can be further suppressed.
  • the median particle size of manganese dioxide is, for example, the median of the particle size distribution determined by quantitative laser diffraction/scattering (qLD) method.
  • qLD quantitative laser diffraction/scattering
  • manganese dioxide separated from the positive electrode removed from a battery can be used as the measurement sample.
  • SALD-7500 nano manufactured by Shimadzu Corporation is used for the measurement.
  • the positive electrode mixture may contain a binder in addition to the positive electrode active material and the oxide of the metal Me.
  • the positive electrode mixture may also contain a conductive agent.
  • binders include fluororesin, rubber particles, and acrylic resin.
  • Examples of conductive agents include conductive carbon materials.
  • Examples of conductive carbon materials include natural graphite, artificial graphite, carbon black, and carbon fiber.
  • the positive electrode may further include a positive electrode current collector that holds the positive electrode mixture.
  • a positive electrode current collector that holds the positive electrode mixture. Examples of materials for the positive electrode current collector include stainless steel, aluminum, and titanium.
  • the positive electrode may be formed by attaching a ring-shaped positive electrode collector with an L-shaped cross section to a positive electrode mixture pellet, or the positive electrode may be formed only from a positive electrode mixture pellet.
  • the positive electrode mixture pellet is obtained, for example, by compression molding a wet positive electrode mixture prepared by adding an appropriate amount of water to the positive electrode active material and additives, and then drying it.
  • a positive electrode having a sheet-shaped positive electrode current collector and a positive electrode mixture layer held on the positive electrode current collector can be used.
  • a perforated current collector is preferable. Examples of perforated current collectors include expanded metal, net, and punched metal.
  • the positive electrode mixture layer can be obtained, for example, by applying the above-mentioned wet positive electrode mixture to the surface of the sheet-shaped positive electrode current collector or filling the positive electrode current collector, pressing in the thickness direction, and drying.
  • the positive electrode preferably comprises a perforated current collector as described above and a positive electrode mixture filled in the current collector.
  • a current collector containing at least one material selected from the group consisting of SUS444, SUS430, and SUS316.
  • the thickness of the positive electrode is, for example, 300 ⁇ m or more and 900 ⁇ m or less.
  • the negative electrode may include, for example, a foil (sheet) of a lithium alloy.
  • the lithium alloy is formed into any shape and thickness depending on the shape, dimensions, specification performance, etc. of the lithium primary battery.
  • the negative electrode may include a negative electrode current collector (e.g., copper foil) that supports the lithium alloy, but may also be a foil (sheet) lithium alloy that does not include a negative electrode current collector.
  • a negative electrode current collector e.g., copper foil
  • the lithium alloy contains Mg
  • the relatively strong Mg remains at the end of discharge, so the negative electrode can be constructed using only a foil (sheet) lithium alloy without using a negative electrode current collector.
  • a lithium alloy containing Mg breakage or partial loss of the negative electrode at the end of discharge, which occurs when the negative electrode does not include a negative electrode current collector, is suppressed.
  • the shape of the negative electrode (lithium alloy) is maintained even at the end of discharge, and the conductivity of the entire negative electrode is ensured even when a negative electrode current collector is not used.
  • a hoop-shaped lithium alloy may be punched into a disk shape and used for the negative electrode.
  • a sheet-shaped lithium alloy may be used for the negative electrode.
  • the sheet may be obtained, for example, by extrusion molding. More specifically, for cylindrical batteries, a lithium alloy foil having a shape with a longitudinal direction and a lateral direction is used.
  • Non-aqueous electrolyte used is a non-aqueous solvent having a lithium salt dissolved therein as a solute.
  • Nonaqueous solvents include organic solvents that can be commonly used in nonaqueous electrolytes for lithium primary batteries.
  • Nonaqueous solvents include ethers, esters, and carbonates.
  • Nonaqueous solvents that can be used include dimethyl ether, ⁇ -butyrolactone, propylene carbonate, ethylene carbonate, and 1,2-dimethoxyethane.
  • the nonaqueous electrolyte may contain one type of nonaqueous solvent, or may contain two or more types of nonaqueous solvents.
  • the non-aqueous solvent contains a cyclic carbonate ester with a high boiling point and a chain ether with low viscosity even at low temperatures.
  • the cyclic carbonate ester preferably contains at least one selected from the group consisting of propylene carbonate (PC) and ethylene carbonate (EC), and PC is particularly preferable.
  • the chain ether preferably has a viscosity of 1 mPa ⁇ s or less at 25°C, and particularly preferably contains dimethoxyethane (DME). The viscosity of the non-aqueous solvent is measured at 25°C at a shear rate of 10,000 (1/s) using a Rheosens m-VROC microsample viscometer.
  • lithium salts examples include LiCF 3 SO 3 , LiClO 4 , LiBF 4 , LiPF 6 , LiRaSO 3 (Ra is a fluorinated alkyl group having 1 to 4 carbon atoms), LiFSO 3 , LiN(SO 2 Rb)(SO 2 Rc) (Rb and Rc are each independently a fluorinated alkyl group having 1 to 4 carbon atoms), LiN(FSO 2 ) 2 , etc.
  • the lithium salts may be used alone or in combination of two or more.
  • the concentration of lithium ions contained in the nonaqueous electrolyte may be, for example, 0.2 mol/L or more and 2.0 mol/L or less, or 0.3 mol/L or more and 1.5 mol/L or less.
  • the non-aqueous electrolyte may contain additives as necessary.
  • additives include phthalimide, N-substituted phthalimide compounds, dimethyl phthalate, phthalate ester compounds, propane sultone, and vinylene carbonate.
  • the total concentration of such additives contained in the non-aqueous electrolyte is, for example, 0.003 to 5 mol/L.
  • a lithium primary battery usually includes a separator interposed between a positive electrode and a negative electrode.
  • a separator a porous sheet formed of an insulating material having resistance to the internal environment of a lithium primary battery may be used.
  • a synthetic resin nonwoven fabric, a synthetic resin microporous film, or a laminate thereof may be used.
  • Synthetic resins used in nonwoven fabrics include, for example, polypropylene, polyphenylene sulfide, and polybutylene terephthalate.
  • Synthetic resins used in microporous membranes include, for example, polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers.
  • Microporous membranes may contain inorganic particles as necessary.
  • the thickness of the separator is, for example, 5 ⁇ m or more and 100 ⁇ m or less.
  • the structure of the lithium primary battery is not particularly limited.
  • the lithium primary battery may be a coin battery equipped with a stacked electrode group configured by stacking a disk-shaped positive electrode and a disk-shaped negative electrode with a separator between them. It may also be a cylindrical battery equipped with a wound electrode group configured by spirally winding a strip-shaped positive electrode and a strip-shaped negative electrode with a separator between them.
  • FIG. 1 shows a front view of a cylindrical lithium primary battery according to one embodiment of the present disclosure, with a portion of the battery in section.
  • a group of electrodes in which a positive electrode 1 and a negative electrode 2 are wound with a separator 3 interposed therebetween, is housed in a battery case 9 together with a non-aqueous electrolyte (not shown).
  • a sealing plate 8 is attached to the opening of the battery case 9.
  • a positive electrode lead 4 connected to the current collector 1a of the positive electrode 1 is connected to the sealing plate 8.
  • a negative electrode lead 5 connected to the negative electrode 2 is connected to the case 9.
  • an upper insulating plate 6 and a lower insulating plate 7 are disposed on the top and bottom of the group of electrodes, respectively, to prevent internal short circuits.
  • the battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte solution
  • the positive electrode includes a positive electrode mixture
  • the positive electrode mixture contains manganese dioxide and an oxide of a metal Me other than manganese,
  • the metal Me has a valence of 2 or more, an ionic radius of 0.8 ⁇ or less, and an electronegativity of 1.65 or less;
  • the amount of the oxide of the metal Me contained in the positive electrode mixture is 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the manganese dioxide contained in the positive electrode mixture
  • the negative electrode includes an alloy including lithium and magnesium, The content of the lithium in the alloy is greater than 88% by weight;
  • the content of the magnesium in the alloy is 0.01% by mass or more and 10% by mass or less.
  • the alloy comprises aluminum; 2.
  • (Technique 5) 5 The lithium primary battery according to any one of claims 1 to 4, wherein the manganese dioxide has a BET specific surface area of 5 m 2 /g or more and 40 m 2 /g or less.
  • the calcined electrolytic manganese dioxide and the oxide of metal Me were mixed and subjected to a composite treatment.
  • a dry particle composite device "Nobilta NOB-130" manufactured by Hosokawa Micron Corporation was used. In this way, a composite material was obtained in which the surface of manganese dioxide particles was covered with the oxide of metal Me.
  • the metal elements shown in the table were used for the metal Me.
  • MgO, Al 2 O 3 , TiO 2 , ZnO, ZrO 2 , Nb 2 O 5 , Y 2 O 3 , MoO 3 , CdO, or In 2 O 3 was used.
  • the positive electrode active material 100 parts by mass of the positive electrode active material were mixed with 3 parts by mass of Ketjen Black, which is a conductive agent, 5 parts by mass of polytetrafluoroethylene, which is a binder, and an appropriate amount of pure water to prepare a wet positive electrode mixture.
  • Ketjen Black which is a conductive agent
  • polytetrafluoroethylene which is a binder
  • pure water 100 parts by mass of the positive electrode active material was mixed with 3 parts by mass of Ketjen Black, which is a conductive agent, 5 parts by mass of polytetrafluoroethylene, which is a binder, and an appropriate amount of pure water to prepare a wet positive electrode mixture.
  • the composite material obtained above or calcined electrolytic manganese dioxide was used as the positive electrode active material.
  • the content of metal Me oxide in the positive electrode mixture was the value shown in the table.
  • the "content of metal Me oxide” in the positive electrode mixture column in the table is the amount (parts by mass) per 100 parts by mass of manganese dioxide contained in the positive electrode mixture.
  • the content of metal Me atoms in the positive electrode mixture was the value shown in the table.
  • the "content of metal Me atoms" in the positive electrode mixture column in the table is the amount (parts by mass) per 100 parts by mass of manganese atoms contained in the positive electrode mixture.
  • the metal Me atoms are derived from the oxide of metal Me, and the manganese atoms are derived from manganese dioxide.
  • the positive electrode mixture was then filled into a positive electrode current collector made of expanded metal of stainless steel (SUS444) with a thickness of 0.4 mm to prepare a positive electrode precursor.
  • the positive electrode precursor was then dried, rolled to a thickness of 0.5 mm using a roll press, and cut to a specified size to obtain a positive electrode.
  • a portion of the filled positive electrode mixture was peeled off, and one end of a stainless steel positive electrode lead was resistance welded to the exposed portion of the positive electrode current collector.
  • a lithium metal foil or a lithium alloy foil (thickness 200 ⁇ m) was cut to a predetermined size to obtain a negative electrode.
  • One end of a nickel negative electrode lead was connected to a predetermined location of the negative electrode by ultrasonic welding.
  • the elements other than Li contained in the lithium alloy foil were Mg and/or Al.
  • the Mg content and Al content in the lithium alloy foil were the values shown in the table. In the table, "-" in the Mg content (or Al content) column means that the Mg content (or Al content) is below the detection limit in composition analysis (ICP emission spectroscopy, etc.).
  • the positive electrode and the negative electrode were wound with a separator interposed therebetween to prepare an electrode group.
  • the separator was a microporous polypropylene film having a thickness of 25 ⁇ m.
  • a non-aqueous solvent was obtained by mixing propylene carbonate (PC), ethylene carbonate (EC), and 1,2-dimethoxyethane (DME) in a volume ratio of 4:2:4. LiCF 3 SO 3 was dissolved in the non-aqueous solvent at a concentration of 0.5 mol/L to prepare a non-aqueous electrolyte solution.
  • PC propylene carbonate
  • EC ethylene carbonate
  • DME 1,2-dimethoxyethane
  • the electrode group was housed in a cylindrical battery case that also served as a negative electrode terminal.
  • An iron case (outer diameter 17 mm, height 45.5 mm) was used as the battery case.
  • a nonaqueous electrolyte was injected into the battery case, and the opening of the battery case was closed using a metal sealing plate that also served as a positive electrode terminal.
  • the other end of the positive electrode lead was connected to the sealing plate, and the other end of the negative electrode lead was connected to the inner bottom surface of the battery case.
  • the battery immediately after assembly was discharged at 2.4 A for 2 minutes, and then aged for 7 days in an atmosphere at 45 ° C.
  • the positive electrode active material after aging was represented by the formula Li x MnO 2 , and the x value indicating the amount of lithium doped was in the range of 0 ⁇ x ⁇ 0.05.
  • the Li x MnO 2 contained in the positive electrode mixture had a median particle diameter of 21 to 23 ⁇ m and a BET specific surface area of 14 to 15 m 2 /g.
  • A1-1 to A1-16, A2-1 to A2-16, A3-1 to A3-16, A3-1 to A3-16, A4-1 to A4-16, A5-1 to A5-16, A6-1 to A6-16, and A7-1 to A7-3 are batteries of the embodiment.
  • B1-1 to B1-7, B2-1 to B2-7, B3-1 to B3-7, B4-1 to B4-7, B5-1 to B5-7, and B6-1 to B6-7 are batteries of the comparative example.
  • R1-1 to R1-3, R2-1 to R2-3, R3-1 to R3-3, R4-1 to R4-3, and R5-1 to R5-3 are batteries of the comparative example.
  • the battery after the aging treatment was stored for 4 months at 70° C.
  • the stored battery was left to stand in an environment of ⁇ 30° C. for 2 hours, and then pulse discharged at 300 mA for 1 second in an environment of ⁇ 30° C., and the minimum voltage at this time was determined as the pulse discharge voltage.
  • Tables 1 to 13 The evaluation results are shown in Tables 1 to 13.
  • the internal resistance is expressed as a relative value when the internal resistance of battery B1-2 is set to 100.
  • the pulse discharge voltage is expressed as a relative value when the pulse discharge voltage of battery B1-2 is set to 100.
  • A7-1 to A7-3 in Table 13 are examples in which an oxide of two types of metals Me was used (a composite material in which the particle surfaces of manganese dioxide are covered with an oxide of two types of metals Me).
  • Batteries A1-1 to A1-16, A2-1 to A2-16, A3-1 to A3-16, A3-1 to A3-16, A4-1 to A4-16, A5-1 to A5-16, and A6-1 to A6-16 showed excellent storage characteristics (Tables 2 to 12).
  • the storage characteristics were deteriorated in the batteries R1-1 to R1-3, B1-1 to B1-7, B2-1 to B2-7, B3-1 to B3-7, B4-1 to B4-7, B5-1 to B5-7, and B6-1 to B6-7.
  • These batteries used a negative electrode with a Li content of 88 mass % or less or a Mg content outside the range of 0.01 to 10 mass %, and/or a positive electrode with a content of metal Me oxide outside the range of 0.1 to 5 parts by mass.
  • the metal Me had an ionic radius greater than 0.8 ⁇ and/or an electronegativity greater than 1.65, and the storage characteristics were deteriorated.
  • the lithium primary battery disclosed herein is suitable for use, for example, as the main power source and memory backup power source for various meters (e.g., smart meters for electricity, water, gas, etc.).
  • meters e.g., smart meters for electricity, water, gas, etc.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56103864A (en) 1980-01-21 1981-08-19 Matsushita Electric Ind Co Ltd Battery
JPS58209862A (ja) 1982-05-13 1983-12-06 レイオバツク・コ−ポレ−シヨン 改良されたリチウム負極
JP2003249213A (ja) 2002-02-25 2003-09-05 Bridgestone Corp リチウム１次電池用の正極及びその製造方法、並びに該正極を備えたリチウム１次電池
WO2003090295A1 (fr) * 2002-04-19 2003-10-30 Bridgestone Corporation Electrode positive pour batterie d'electrolyte non aqueux, son procede de production et batterie d'electrolyte non aqueux
JP2010250969A (ja) * 2009-04-10 2010-11-04 Panasonic Corp リチウム電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56103864A (en) 1980-01-21 1981-08-19 Matsushita Electric Ind Co Ltd Battery
JPS58209862A (ja) 1982-05-13 1983-12-06 レイオバツク・コ−ポレ−シヨン 改良されたリチウム負極
JP2003249213A (ja) 2002-02-25 2003-09-05 Bridgestone Corp リチウム１次電池用の正極及びその製造方法、並びに該正極を備えたリチウム１次電池
WO2003090295A1 (fr) * 2002-04-19 2003-10-30 Bridgestone Corporation Electrode positive pour batterie d'electrolyte non aqueux, son procede de production et batterie d'electrolyte non aqueux
JP2010250969A (ja) * 2009-04-10 2010-11-04 Panasonic Corp リチウム電池

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