WO2024043272A1 - リチウム一次電池 - Google Patents

リチウム一次電池 Download PDF

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WO2024043272A1
WO2024043272A1 PCT/JP2023/030294 JP2023030294W WO2024043272A1 WO 2024043272 A1 WO2024043272 A1 WO 2024043272A1 JP 2023030294 W JP2023030294 W JP 2023030294W WO 2024043272 A1 WO2024043272 A1 WO 2024043272A1
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mass
lithium
primary battery
positive electrode
group
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French (fr)
Japanese (ja)
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仁志 西谷
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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 JP2024542849A priority Critical patent/JPWO2024043272A1/ja
Priority to EP23857380.2A priority patent/EP4579776A4/en
Priority to CN202380059601.7A priority patent/CN119731792A/zh
Publication of WO2024043272A1 publication Critical patent/WO2024043272A1/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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/5835—Comprising fluorine or fluoride salts
    • 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
    • H01M4/405—Alloys based on lithium
    • 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
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Definitions

  • the present disclosure relates to a lithium primary battery.
  • Lithium primary batteries have high energy density and low self-discharge, so they are used as power sources for many electronic devices.
  • Manganese dioxide or the like is used for the positive electrode of a lithium primary battery.
  • sheet-like (foil-like) metallic lithium or lithium alloy is used for the negative electrode of a lithium primary battery.
  • Patent Document 1 in a lithium-organic electrolyte battery in which a lithium salt is dissolved in an electrolyte and a separator is opposed to a negative electrode, a coating layer of an aluminum-magnesium alloy is initially laminated on the surface of the lithium body adjacent to the separator.
  • a lithium negative electrode has been proposed in which aluminum-magnesium-lithium ternary alloy is formed by diffusion, increasing the negative electrode surface area and improving the pulse performance of the battery.
  • WO 03/03002 includes a cathode assembly, the cathode assembly consisting of a metal cathode current collector having two major surfaces and a cathode cladding disposed on at least one of the two major surfaces;
  • An electrochemical cell is proposed, further comprising a metallic lithium anode, the coating comprising iron disulfide and alloyed with aluminum, wherein the anode to cathode input ratio is less than or equal to 1.0.
  • Patent Document 3 discloses a positive electrode using iron disulfide as a positive electrode active material, a negative electrode using a lithium alloy as a negative electrode active material, an electrode group in which the positive electrode and the negative electrode are wound together with a separator interposed therebetween, and non-aqueous electrolysis.
  • a lithium primary battery has been proposed that includes a liquid and a lithium alloy in which the lithium alloy contains 0.02 to 0.2 mol % of at least one of magnesium and tin.
  • battery capacity may decrease due to deterioration of the negative electrode.
  • One aspect of the present disclosure includes a positive electrode, a negative electrode, and a nonaqueous electrolyte, the positive electrode containing at least one selected from the group consisting of manganese dioxide and graphite fluoride, and the negative electrode containing lithium
  • the lithium alloy contains aluminum, magnesium, and at least one selected from the group consisting of sodium and calcium, and the total content of the aluminum and magnesium in the lithium alloy is:
  • the present invention relates to a lithium primary battery in which the total content of the sodium and calcium in the lithium alloy is 0.02% by mass or more and 10% by mass or less, and the total content of the sodium and calcium in the lithium alloy is 0.02% 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.
  • a lithium primary battery includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
  • the positive electrode contains at least one member selected from the group consisting of manganese dioxide and graphite fluoride.
  • the negative electrode includes a lithium alloy, and the lithium alloy includes at least one selected from the group consisting of aluminum (Al), magnesium (Mg), sodium (Na), and calcium (Ca).
  • Al aluminum
  • Mg magnesium
  • Na sodium
  • Ca calcium
  • the total content of Al and Mg in the lithium alloy is 0.02% by mass or more and 10% by mass or less.
  • the total content of Na and Ca in the lithium alloy is 0.02% by mass or less.
  • Al, Mg, and at least one selected from the group consisting of Na and Ca are mixed.
  • the lithium alloy contains Al
  • side reactions due to contact between the negative electrode and the non-aqueous electrolyte are suppressed, and capacity reduction due to the side reactions is suppressed.
  • Al tends to segregate in lithium alloys, and due to the segregation of Al, the consumption of Li on the negative electrode surface becomes uneven during discharge, causing part of the negative electrode to be chipped or broken at the end of discharge, resulting in a decrease in capacity. There is.
  • the dispersibility of Mg is improved, and the above-mentioned Al segregation due to Mg is improved. A significant suppressing effect is obtained, and a decrease in capacity is significantly suppressed. Therefore, high capacity can be obtained both initially and after long-term storage, and the rate of capacity deterioration after storage can be significantly reduced.
  • the total content of Na and Ca in the lithium alloy is 0.02% by mass or less, trace amounts of Na and/or Ca are easily dissolved in the lithium alloy and uniformly dispersed, improving the dispersibility of Mg. can contribute stably and efficiently to
  • the total content of Al and Mg in the lithium alloy is less than 0.02% by mass, the effects of Al and Mg will be insufficient and the capacity will tend to decrease.
  • the total content of Al and Mg in the lithium alloy is greater than 10% by mass, and/or when the total content of Na and Ca in the lithium alloy is greater than 0.02% by mass, the negative electrode Since the amount of Li occupied decreases and the absolute amount of Li decreases, the capacity may decrease.
  • Na and/or Ca become difficult to dissolve in the lithium alloy, the dispersibility of Mg decreases, and the capacity decreases.
  • the lithium alloy used for the negative electrode is, for example, in the form of a foil (sheet). From the viewpoint of increasing capacity, the content of Li in the lithium alloy may be, for example, 90% by mass or more, or 95% by mass or more.
  • the lithium alloy contains Al, Mg, and at least one selected from the group consisting of Na and Ca.
  • the total content of Al and Mg in the lithium alloy is 0.02 mass% or more and 10 mass% or less, and 0.05 mass% or more (or 0.1 mass% or more) and 8 mass% or less. It may be 0.1% by mass or more (or 0.2% by mass or more) and 5% by mass or less.
  • the Mg content (or Al content) in the lithium alloy may be 0.02% by mass or more, 0.05% by mass or more, or 0.1% by mass or more (or 0.2% by mass). mass% or more). Further, the Mg content (or Al content) in the lithium alloy may be 9.5% by mass or less, 7% by mass or less, 5% by mass or less, 2 It may be less than % by mass.
  • the molar ratio of Mg to Al: Mg/Al may be, for example, 0.01 or more (or 0.02 or more) and 100 or less, or 0.05 or more and 20 or less.
  • the total content of Na and Ca in the lithium alloy is 0.02% by mass or less, and may be 0.0005% by mass or more and 0.019% by mass or less, 0.001% by mass or more, and 0.01% by mass or more. It may be .018% by mass or less.
  • the Na content (or Ca content) in the lithium alloy may be 0.0001% by mass or more, 0.0005% by mass or more, or 0.0025% by mass or more. . Further, the Na content (or Ca content) in the lithium alloy may be 0.015% by mass or less, 0.012% by mass or less, and 0.010% by mass or less. Good too.
  • the lithium alloy may contain metal elements other than Li, Al, Mg, Na, and Ca.
  • metal elements include Sn, Ni, Pb, In, K, Fe, and Si.
  • the total content of metal elements other than lithium in the lithium alloy is 0.05% by mass or more and 15% by mass or less (or 10% by mass or less) from the viewpoint of ensuring discharge capacity and stabilizing internal resistance. It is preferable that there be.
  • the content of each element in the lithium alloy is determined by inductively coupled plasma (ICP) emission spectrometry or atomic absorption spectrometry (AAS).
  • ICP inductively coupled plasma
  • AAS atomic absorption spectrometry
  • the non-aqueous electrolyte preferably contains at least one additive selected from the group consisting of cyclic imide compounds, phthalate compounds, and isocyanate compounds.
  • a composite film containing Al and Mg derived from the lithium alloy and components derived from the additive can be formed on the surface of the lithium alloy (negative electrode) containing Al and Mg. .
  • the coating has excellent chemical stability, and since the coating contains Al and Mg derived from a lithium alloy, the wettability of the negative electrode with respect to the non-aqueous electrolyte is improved, and the resistance of the negative electrode is reduced.
  • the coating facilitates more uniform consumption of Li on the surface of the negative electrode.
  • the lithium alloy further contains at least one of Na and Ca, Mg is more uniformly dispersed, and the uniformity is further improved in the entire negative electrode. Therefore, the above film is easily formed stably. As a result, a decrease in capacity can be further suppressed.
  • the content of the additive in the non-aqueous electrolyte is, for example, 0.01% by mass or more and 5% by mass or less.
  • the content of the additive in the non-aqueous electrolyte is the mass ratio (percentage) of the additive to the entire non-aqueous electrolyte.
  • it is desirable that the content of the additive in the non-aqueous electrolyte is within the above range immediately after manufacturing the battery (or at the time of preparing the non-aqueous electrolyte).
  • some of the additives are consumed in forming a film, and the content of additives in the non-aqueous electrolyte is smaller than the above range.
  • cyclic imide compound examples include cyclic diacylamine compounds.
  • the cyclic imide compound should just have a diacylamine ring (hereinafter also referred to as an imide ring).
  • Another ring hereinafter also referred to as a second ring
  • the cyclic imide compound may be contained in the nonaqueous electrolyte in the form of an imide, an anion, or a salt.
  • the cyclic imide compound When the cyclic imide compound is contained in the non-aqueous electrolyte in the form of an imide, it may be contained in a form having a free NH group, or may be contained in the form of a tertiary amine.
  • Examples of the second ring include aromatic rings, saturated or unsaturated aliphatic rings, and the like.
  • the second ring may include at least one heteroatom.
  • heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms.
  • Examples of the cyclic imide compound include an aliphatic dicarboxylic acid imide compound and a cyclic imide compound having a second ring.
  • Examples of the aliphatic dicarboxylic acid imide compound include succinimide.
  • Examples of the cyclic imide compound having a second ring include imide compounds of aromatic or alicyclic dicarboxylic acids. Examples of aromatic dicarboxylic acids and alicyclic dicarboxylic acids include those having carboxy groups on two adjacent atoms constituting a ring.
  • Examples of the cyclic imide compound having a second ring include phthalimide and a hydrogenated product of phthalimide. Examples of hydrogenated products of phthalimide include cyclohex-3-ene-1,2-dicarboximide and cyclohexane-1,2-dicarboximide.
  • the imide ring may be an N-substituted imide ring having a substituent on the nitrogen atom of the imide.
  • substituents include hydroxy groups, alkyl groups, alkoxy groups, and halogen atoms.
  • alkyl group include C1 to C4 alkyl groups, and may also be methyl groups, ethyl groups, and the like.
  • alkoxy group include C1 to C4 alkoxy groups, and may also be methoxy groups, ethoxy groups, and the like.
  • the halogen atom include a chlorine atom and a fluorine atom.
  • the cyclic imide compound is preferably at least one selected from the group consisting of phthalimide and N-substituted phthalimide.
  • the substituent on the nitrogen atom of the N-substituted phthalimide can be selected from the substituents exemplified for the N-substituted imide ring.
  • the N-substituted phthalimide includes, for example, at least one selected from the group consisting of N-hydroxyphthalimide, N-(2-hydroxyethyl)phthalimide, N-(cyclohexylthio)phthalimide, and N-(phenylthio)phthalimide. It is preferable. Phthalimide and/or N-substituted phthalimide may account for 50% by weight or more, even 70% by weight or more, or 90% by weight or more of the cyclic imide compound.
  • the nonaqueous electrolyte may contain one type of cyclic imide compound, or may contain two or more types of cyclic imide compounds.
  • the content of the cyclic imide compound in the non-aqueous electrolyte may be 1% by mass or less, 0.001% by mass or more and 1% by mass or less, 0.001% by mass or more, 0. It may be 8% by mass or less.
  • Phthalate compounds include phthalate esters and derivatives thereof.
  • the derivative may have a substituent attached to the aromatic ring derived from phthalic acid.
  • substituents include hydroxy groups, alkyl groups, alkoxy groups, and halogen atoms.
  • alkyl group include C1 to C4 alkyl groups, and may also be methyl groups, ethyl groups, and the like.
  • alkoxy group include C1 to C4 alkoxy groups, and may also be methoxy groups, ethoxy groups, and the like.
  • the halogen atom include a chlorine atom and a fluorine atom.
  • the phthalate ester compound may be a phthalate monoester compound, but a phthalate diester compound is preferable from the viewpoint that the resulting film can easily protect the Li alloy surface.
  • the alcohol constituting the ester with phthalic acid (or its derivative) is preferably a C1 to C20 (preferably C1 to C6) saturated or unsaturated aliphatic alcohol.
  • phthalate diester compounds include dimethyl phthalate, diethyl phthalate, diallyl phthalate, dibutyl phthalate, diisobutyl phthalate, bis(2-ethylhexyl) phthalate, and the like. These may be used alone or in combination of two or more.
  • the phthalate diester compound may account for 50% by mass or more, further 70% by mass or more, or 90% by mass or more of the phthalate ester compound.
  • the non-aqueous electrolyte may contain one type of phthalate ester compound, or may contain two or more types.
  • the content of the phthalate ester compound in the non-aqueous electrolyte may be 1% by mass or less, or 0.1% by mass or more and 1% by mass or less.
  • the isocyanate compound has, for example, at least one isocyanate group and a C1 to C20 aliphatic hydrocarbon group or a C6 to C20 aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group and aromatic hydrocarbon group constituting the isocyanate compound may have a substituent.
  • the substituent may be any group that can exist stably, such as a halogen atom or a nitrile group.
  • the aliphatic group may be an alicyclic aliphatic group, or a linear or branched aliphatic group.
  • the aromatic hydrocarbon group is a hydrocarbon group having one or more aromatic rings, and may be a group in which an aromatic ring and an aliphatic group are connected.
  • the isocyanate compound may be a monoisocyanate compound having one isocyanate group, but preferably a diisocyanate compound having two isocyanate groups.
  • Diisocyanate compounds are believed to produce composite coatings with greater chemical stability than monoisocyanate compounds, and with lower resistance than triisocyanates. Further, diisocyanate compounds have a high ability to form a composite film even in small amounts, and have excellent stability within a battery.
  • diisocyanate compounds include compounds represented by OCN-C n H 2n -NCO (n is an integer of 1 to 10) (for example, hexamethylene diisocyanate), compounds having an alicyclic diyl group ( For example, 1,3-bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane-4,4'-diisocyanate, bicyclo[2.2.1]heptane-2,5-diylbis(methylisocyanate), bicyclo[2.2.
  • at least one selected from the group consisting of hexamethylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and isophorone diisocyanate is preferred. These may account for 50% by mass or more, further 70% by mass or more, or 90% by mass or more of the isocyanate compound.
  • the diisocyanate compounds When adding a diisocyanate compound to the non-aqueous electrolyte, the diisocyanate compounds may react with each other in the battery (in the non-aqueous electrolyte) to form an isocyanurate, a urea, or a bullet. Therefore, when a battery is disassembled and a non-aqueous electrolyte is analyzed, isocyanurate bodies, urea bodies, and bullet bodies derived from diisocyanate compounds may be detected.
  • the non-aqueous electrolyte may contain one type of isocyanate compound, or may contain two or more types of isocyanate compounds.
  • the content of the isocyanate compound in the non-aqueous electrolyte may be 3% by mass or less, 0.01% by mass or more and 2% by mass or less, 0.01% by mass or more and 1.5% by mass. It may be less than % by mass.
  • liquid chromatography mass spectrometry LC/MS
  • gas chromatography mass spectrometry GC/MS
  • UV Ultraviolet spectroscopy
  • NMR nuclear magnetic resonance spectroscopy
  • IR infrared absorption spectroscopy
  • MS mass spectrometry
  • the positive electrode contains at least one selected from the group consisting of manganese dioxide and graphite fluoride as a positive electrode active material. When this positive electrode is used, it is advantageous in terms of improving capacity both initially and after long-term storage. As manganese dioxide, electrolytic manganese dioxide is preferably used. A positive electrode containing manganese dioxide develops a relatively high voltage and is advantageous in improving discharge characteristics (pulse discharge characteristics). Manganese dioxide may be in a mixed crystal state including multiple types of crystal states. The positive electrode may contain manganese oxides other than manganese dioxide.
  • manganese oxides other than manganese dioxide examples include MnO, Mn 3 O 4 , Mn 2 O 3 , Mn 2 O 7 and the like. It is preferable that the main component of the manganese oxide contained in the positive electrode is manganese dioxide.
  • the main component here means that the proportion of manganese dioxide in the manganese oxide is 50% by mass or more.
  • the proportion of manganese dioxide in the manganese oxide may be 70% by mass or more, or 90% by mass or more.
  • iron disulfide is used as a positive electrode active material for a negative electrode containing the above lithium alloy, the capacity may decrease after long-term storage.
  • Fe and S are eluted from the positive electrode containing iron disulfide and cause a side reaction with Al and Mg in the negative electrode (lithium alloy), and due to this side reaction, a film containing Fe and S is formed on the surface of the negative electrode. It is presumed that this is due to the non-uniformity of the negative electrode reaction due to the coating.
  • the positive electrode may include a positive electrode mixture containing a positive electrode active material, a binder, a conductive agent, and the like.
  • the binder include fluororesins such as polytetrafluoroethylene, rubber particles, and acrylic resins.
  • the conductive agent include conductive carbon materials. Examples of the conductive carbon material include natural graphite, artificial graphite, carbon black, and carbon fiber.
  • the positive electrode may further include a positive electrode current collector that holds a positive electrode mixture.
  • a positive electrode current collector that holds a positive electrode mixture.
  • Examples of the material of the positive electrode current collector include stainless steel, aluminum, and titanium.
  • the positive electrode may be constructed by attaching a ring-shaped positive electrode current collector with an L-shaped cross section to the positive electrode mixture pellet, or the positive electrode may be constructed only from the positive electrode mixture pellet.
  • the positive electrode mixture pellets can be obtained, for example, by compression molding a wet positive electrode mixture prepared by adding an appropriate amount of water to a positive electrode active material, and then drying.
  • a positive electrode including a sheet-like 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.
  • the perforated current collector include expanded metal, net, punched metal, and the like.
  • the positive electrode mixture layer can be obtained, for example, by applying the above-mentioned wet positive electrode mixture onto the surface of a sheet-like positive electrode current collector or filling the positive electrode current collector, applying pressure in the thickness direction, and drying.
  • the negative electrode contains the lithium alloy described above.
  • the lithium alloy is molded into any shape and thickness depending on the shape, dimensions, standard performance, etc. of the lithium primary battery. Since the lithium alloy contains Mg and relatively strong Mg remains at the end of discharge, the negative electrode can be constructed using only the lithium alloy sheet (foil) without using a current collector such as copper foil.
  • the Li in the negative electrode can be used effectively, so compared to metallic lithium or a lithium alloy containing only one of Al and Mg, the discharge Capacity can be increased.
  • a hoop-shaped lithium alloy punched out into a disk shape may be used for the negative electrode.
  • a sheet-like lithium alloy may be used for the negative electrode. The sheet is obtained, for example, by extrusion molding. More specifically, in a cylindrical battery, a lithium alloy foil or the like having a shape having a longitudinal direction and a transverse direction is used.
  • the non-aqueous electrolyte includes, for example, a non-aqueous solvent and a lithium salt.
  • concentration of lithium ions (total concentration of lithium salts) contained in the non-aqueous electrolyte is, for example, 0.2 mol/L or more and 2.0 mol/L or less, and 0.3 mol/L or more and 1.5 mol/L. It may be the following.
  • non-aqueous solvent examples include organic solvents that can generally be used in non-aqueous electrolytes of lithium primary batteries.
  • examples of the nonaqueous solvent include ether, ester, carbonate ester, and the like.
  • examples of non-aqueous solvents include dimethyl ether, ⁇ -butyl lactone, propylene carbonate (PC), ethylene carbonate (EC), dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane (DME), and 1,2-dimethoxyethane (DME). Ethoxyethane, methyl acetate, ethyl acetate, propyl acetate, etc. can be used.
  • the non-aqueous electrolyte may contain one type of non-aqueous solvent, or may contain two or more types of non-aqueous solvents.
  • the nonaqueous solvent preferably contains a cyclic carbonate ester with a high boiling point and a chain ether that has a low viscosity even at low temperatures.
  • the cyclic carbonate preferably contains at least one selected from the group consisting of PC and EC, with PC being particularly preferred. It is preferable that the chain ether contains DME.
  • lithium salts examples include lithium salts used as solutes in lithium primary batteries.
  • lithium salts 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).
  • Rb and Rc are each independently a fluorinated alkyl group having 1 to 4 carbon atoms
  • LiN(FSO 2 ) 2 LiN(SO 2 CF 3 ) 2
  • LiN(SO 2 F) (POF 2 ) LiPO 2 F 2
  • LiB(C 2 O 4 ) 2 LiBF 2 (C 2 O 4 ).
  • at least one selected from the group consisting of LiCF 3 SO 3 , LiBF 4 , and LiN(FSO 2 ) 2 is preferable.
  • the non-aqueous electrolyte may contain one or more of these lithium salts.
  • the non-aqueous electrolyte may further contain other components such as the above-mentioned additives.
  • Ingredients other than the above additives include propane sultone, propene sultone, ethylene sulfite, 3,2-dioxathiolane-2,2-dioxide, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, adiponitrile, succino Examples include nitrile and succinic anhydride.
  • the other components may be lithium salts or may be capable of generating lithium ions.
  • a lithium primary battery usually includes a separator interposed between a positive electrode and a negative electrode.
  • a porous sheet made of an insulating material that is resistant to the internal environment of the lithium primary battery may be used.
  • nonwoven fabrics made of synthetic resin, microporous membranes made of synthetic resin, or laminates thereof may be used.
  • Examples of the synthetic resin used for the nonwoven fabric include polypropylene, polyphenylene sulfide, and polybutylene terephthalate.
  • Examples of the synthetic resin used in the microporous membrane include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers.
  • the microporous membrane may contain inorganic particles if 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-shaped battery including a stacked electrode group configured by stacking a disc-shaped positive electrode and a disc-shaped negative electrode with a separator in between. It may be a cylindrical battery including a wound electrode group configured by spirally winding a band-shaped positive electrode and a band-shaped negative electrode with a separator in between.
  • FIG. 1 shows a partially sectional front view of a lithium primary battery according to an embodiment of the present disclosure.
  • an electrode group including a positive electrode 1 and a negative electrode 2 wound together with a separator 3 in between 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 a battery case 9.
  • an upper insulating plate 6 and a lower insulating plate 7 are arranged at the upper and lower parts of the electrode group, respectively, to prevent internal short circuits.
  • the following techniques are disclosed by the description of the above embodiments.
  • the positive electrode includes at least one selected from the group consisting of manganese dioxide and graphite fluoride
  • the negative electrode includes a lithium alloy
  • the lithium alloy contains aluminum, magnesium, at least one member selected from the group consisting of sodium and calcium,
  • the total content of the aluminum and magnesium in the lithium alloy is 0.02% by mass or more and 10% by mass or less
  • a lithium primary battery wherein the total content of the sodium and calcium in the lithium alloy is 0.02% by mass or less.
  • (Technology 2) The lithium primary battery according to technique 1, wherein the total content of the aluminum and the magnesium in the lithium alloy is 0.05% by mass or more and 8% by mass or less.
  • (Technology 3) The lithium primary battery according to technology 1 or 2, wherein the total content of the sodium and calcium in the lithium alloy is 0.001% by mass or more and 0.018% by mass or less.
  • (Technology 4) The lithium primary battery according to any one of Techniques 1 to 3, wherein the nonaqueous electrolyte contains at least one additive selected from the group consisting of a cyclic imide compound, a phthalate compound, and an isocyanate compound. .
  • a positive electrode current collector made of expanded metal made of stainless steel (SUS444) with a thickness of 0.1 mm was filled with the positive electrode mixture to prepare a positive electrode precursor. Thereafter, the positive electrode precursor was dried, rolled using a roll press, and cut into a size of 3.5 cm in length and 20 cm in width to obtain a positive electrode. Subsequently, a portion of the filled positive electrode mixture was peeled off, and one end of a positive electrode lead made of SUS444 was resistance welded to the exposed portion of the positive electrode current collector.
  • a negative electrode was obtained by cutting lithium alloy foil (thickness: 250 ⁇ m) into a size of 3.7 cm in length and 22 cm in width. One end of a nickel negative electrode lead was connected to a predetermined location of the negative electrode by pressure welding.
  • the lithium alloy foil used had a content of Al, Mg, Na, and Ca each having the values shown in Table 1.
  • the content of Al, etc. in the lithium alloy is determined by ICP emission spectrometry or atomic absorption spectrometry, and "-" in the column for the content of Al, etc. in the lithium alloy indicates that Al, etc. was detected by ICP emission spectrometry or atomic absorption spectrometry. indicates that it was not done.
  • An electrode group was produced by winding a positive electrode and a negative electrode with a separator in between.
  • a microporous polypropylene membrane having a thickness of 25 ⁇ m was used as the separator.
  • LiCF 3 SO 3 was dissolved in a mixed solvent of PC, EC, and DME (volume ratio 3:2:5) at a concentration of 0.5 mol/L to prepare a non-aqueous electrolyte.
  • 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.
  • the opening of the battery case was closed using a metal sealing plate that also served as a positive 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. In this way, a lithium primary battery was produced.
  • A1 to A8 in Table 1 are the batteries of Examples 1 to 8.
  • B1 to B13 are batteries of Comparative Examples 1 to 13.
  • Capacity after storage The aged battery was stored in an environment of 85° C. for 3 months. After storage, the battery was subjected to constant current discharge at 2.5 mA in an environment of 20°C until the battery voltage reached 0.9V. The discharge time at this time was measured, and the capacity after storage was determined.
  • batteries A1 to A7 had larger initial and storage capacities, lower capacity deterioration rates, and suppressed capacity decline after high-temperature storage.
  • battery B13 using iron disulfide as the positive electrode active material the capacity after storage decreased significantly and the rate of capacity deterioration increased significantly.
  • batteries A1 to A7 containing a small amount of at least one of Na and Ca in the Li-Al-Mg alloy have larger initial and storage capacities than battery B3. , the capacity deterioration rate was small.
  • the capacity deterioration rate of batteries A1 to A7 is 5.5% to 5.6%
  • the capacity deterioration rate of battery B3 is 7.5%
  • the improvement range of the capacity deterioration rate of batteries A1 to A7 relative to battery B3 is , about 25% to about 27% (B3 ⁇ A1 to A7).
  • the improvement in the capacity deterioration rate of battery A1 relative to battery B3 is calculated from ⁇ (7.5-5.6)/7.5 ⁇ 100.
  • the positive electrode active material is manganese dioxide
  • the Li alloy contains Al and Mg in a total of 0.02 to 10% by mass.
  • a lithium alloy contains Al and Mg in a total amount of 0.02% by mass or more and 10% by mass or less, by including a small amount of at least one of Na and Ca in the lithium alloy, initial and storage It can be seen that a battery with a large capacity and a low rate of capacity deterioration can be obtained.
  • Examples 9 to 17 ⁇ In the production of the negative electrode, lithium alloy foils were used in which the contents of Al, Mg, Na, and Ca were as shown in Table 2. In preparing the non-aqueous electrolyte, additives were further included in the non-aqueous electrolyte as necessary. The compounds shown in Table 2 were used as additives. The content (mass%) of the additive in the non-aqueous electrolyte was set to the values shown in Table 2. Batteries A9 to A17 of Examples 9 to 17 were produced and evaluated in the same manner as Battery A1 of Example 1 except for the above.
  • All of the batteries A9 to A17 had large initial capacities and capacities after storage, and had small capacity deterioration rates. In batteries A10 to A17 in which the non-aqueous electrolyte contained additives, the capacity deterioration rate was further reduced.
  • the lithium primary battery of the present disclosure is suitably used, for example, as a main power source or memory backup power source for various meters (for example, smart meters for electricity, water, gas, etc.).

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JPH0337964A (ja) * 1989-06-30 1991-02-19 Sanyo Electric Co Ltd 非水電解液電池
JP2010232039A (ja) * 2009-03-27 2010-10-14 Sanyo Electric Co Ltd 非水電解質一次電池
JP2011192627A (ja) * 2010-02-22 2011-09-29 Enax Inc 高温用リチウム電池
WO2012066709A1 (ja) 2010-11-15 2012-05-24 パナソニック株式会社 リチウム一次電池
JP2013513207A (ja) * 2009-12-04 2013-04-18 イーグルピッチャー テクノロジーズ，エルエルシー フッ化炭素カソード物質の混合物を有する非水セル
WO2013058224A1 (ja) * 2011-10-17 2013-04-25 宇部興産株式会社 非水電解液及びそれを用いた蓄電デバイス
JP2020530937A (ja) * 2017-08-15 2020-10-29 ハイドロ−ケベック リチウムベースの合金の形態における電極材料およびそれを製造するための方法
WO2022138490A1 (ja) * 2020-12-25 2022-06-30 パナソニックＩｐマネジメント株式会社 リチウム二次電池

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JPH0337964A (ja) * 1989-06-30 1991-02-19 Sanyo Electric Co Ltd 非水電解液電池
JP2010232039A (ja) * 2009-03-27 2010-10-14 Sanyo Electric Co Ltd 非水電解質一次電池
JP2013513207A (ja) * 2009-12-04 2013-04-18 イーグルピッチャー テクノロジーズ，エルエルシー フッ化炭素カソード物質の混合物を有する非水セル
JP2011192627A (ja) * 2010-02-22 2011-09-29 Enax Inc 高温用リチウム電池
WO2012066709A1 (ja) 2010-11-15 2012-05-24 パナソニック株式会社 リチウム一次電池
WO2013058224A1 (ja) * 2011-10-17 2013-04-25 宇部興産株式会社 非水電解液及びそれを用いた蓄電デバイス
JP2020530937A (ja) * 2017-08-15 2020-10-29 ハイドロ−ケベック リチウムベースの合金の形態における電極材料およびそれを製造するための方法
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