WO2023163135A1 - 円筒形リチウム二次電池 - Google Patents

円筒形リチウム二次電池 Download PDF

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Publication number
WO2023163135A1
WO2023163135A1 PCT/JP2023/006877 JP2023006877W WO2023163135A1 WO 2023163135 A1 WO2023163135 A1 WO 2023163135A1 JP 2023006877 W JP2023006877 W JP 2023006877W WO 2023163135 A1 WO2023163135 A1 WO 2023163135A1
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Prior art keywords
secondary battery
lithium secondary
aqueous electrolyte
negative electrode
lithium
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PCT/JP2023/006877
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English (en)
French (fr)
Japanese (ja)
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聡 蚊野
貴弘 井上
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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 CN202380016589.1A priority Critical patent/CN118541841A/zh
Priority to US18/841,482 priority patent/US20250038314A1/en
Priority to EP23760133.1A priority patent/EP4489164A4/en
Priority to JP2024503277A priority patent/JPWO2023163135A1/ja
Publication of WO2023163135A1 publication Critical patent/WO2023163135A1/ja
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to cylindrical lithium secondary batteries.
  • a lithium secondary battery (lithium metal secondary battery) is promising as a high-capacity non-aqueous electrolyte secondary battery that exceeds that of lithium-ion batteries.
  • lithium metal deposits on the negative electrode during charging, and the lithium metal dissolves in the non-aqueous electrolyte during discharging.
  • Patent Document 1 describes a non-aqueous electrolyte battery in which metallic lithium is used as a negative electrode active material, copper oxide is used as a positive electrode active material, and a non-aqueous solvent is used as an electrolytic solution.
  • Non-aqueous electrolyte battery characterized in that it is regulated to 0.15 ⁇ L or more per unit; We are proposing an electrolyte battery.
  • Patent Document 2 describes a non-aqueous electrolyte secondary battery comprising an electrode group having a positive electrode plate, a negative electrode plate and a separator, and a non-aqueous electrolyte, wherein the amount of the non-aqueous electrolyte is 1.3 to 1.3 per mAh discharge capacity.
  • a nonaqueous electrolyte secondary battery with a capacity of 1.8 ⁇ L is proposed.
  • lithium metal Since lithium metal is highly active, lithium metal deposits on the negative electrode during charging and dissolves into the non-aqueous electrolyte during discharging. reaction) easily proceeds. In addition to the consumption of the non-aqueous electrolyte due to side reactions, the negative electrode of the lithium secondary battery expands and contracts significantly, so local drying of the non-aqueous electrolyte tends to occur. Therefore, the capacity of the lithium secondary battery tends to decrease.
  • One aspect of the present invention includes a bottomed cylindrical battery case having an opening, a wound electrode group and a non-aqueous electrolyte housed in the battery case, and a sealing member that seals the opening.
  • the wound electrode group includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and in the negative electrode, lithium metal is deposited by charging and discharging.
  • the lithium metal is dissolved in the non-aqueous electrolyte
  • the non-aqueous electrolyte contains an electrolyte salt and a solvent
  • the solvent contains an ether compound as a main component
  • the discharge capacity of the lithium secondary battery is
  • the amount of the non-aqueous electrolyte per 1 mAh is 2.5 ⁇ L (microliter) or more and 6.5 ⁇ L or less, and relates to the cylindrical lithium secondary battery.
  • FIG. 1 is a schematic longitudinal sectional view of a cylindrical lithium secondary battery according to one embodiment of the present invention.
  • a cylindrical lithium secondary battery includes a bottomed cylindrical battery case having an opening, a wound electrode group and a non-aqueous electrolyte housed in the battery case, and sealing the opening. and a sealing member (or a sealing plate).
  • the cylindrical shape means a shape having a cylindrical cylindrical portion.
  • the outer shape of the cross section of the cylindrical portion perpendicular to the winding axis of the electrode group does not have to be strictly circular, and may be elliptical or the like.
  • the sealing member may have any shape as long as it conforms to the shape of the opening, and may be disk-shaped.
  • a wound electrode group includes a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode.
  • the wound electrode group is configured by winding a positive electrode and a negative electrode around a predetermined winding core with a separator interposed therebetween.
  • the positive electrode, negative electrode and separator may each be in the form of a long sheet, for example.
  • the winding core is usually extracted from the center of the electrode group.
  • a lithium secondary battery according to the present disclosure is also referred to as a lithium metal secondary battery.
  • the negative electrode has at least a negative electrode current collector, and lithium metal is directly or indirectly deposited on the negative electrode current collector.
  • the negative electrode according to the present disclosure differs from a negative electrode in which electron movement in the negative electrode during charge and discharge is mainly due to lithium ion absorption and release by the negative electrode active material (such as graphite).
  • the open circuit voltage (OCV: Open Circuit Voltage) of the negative electrode when fully charged is, for example, 70 mV or less with respect to lithium metal (lithium dissolution deposition potential).
  • a fully charged state is a state in which the battery is charged to a state of charge (SOC) of, for example, 0.98 ⁇ C or more, where C is the rated capacity of the battery.
  • SOC state of charge
  • the open circuit potential (OCV) of the negative electrode when fully charged can be measured by disassembling a fully charged battery in an argon atmosphere, taking out the negative electrode, and assembling a cell using lithium metal as a counter electrode.
  • the non-aqueous electrolyte of the cell may be of the same composition as the non-aqueous electrolyte in the disassembled battery.
  • a non-aqueous electrolyte includes an electrolyte salt and a solvent.
  • a solvent contains an ether compound as a main component.
  • the main component means a component that accounts for 50% by mass or more, further 70% by mass or more of the solvent.
  • the ether compound content in the non-aqueous electrolyte may be, for example, 80% by mass or more. Since the ether compound is unlikely to cause a side reaction between the non-aqueous electrolyte and highly active lithium metal, consumption of the non-aqueous electrolyte due to side reactions is suppressed. Therefore, even if the negative electrode expands significantly, the non-aqueous electrolyte is less likely to dry up locally. Therefore, the decrease in capacity of the lithium secondary battery due to charge/discharge cycles is suppressed.
  • the amount of non-aqueous electrolyte per 1 mAh discharge capacity of the lithium secondary battery is controlled to 2.5 ⁇ L or more and 6.5 ⁇ L or less (preferably 2.9 ⁇ L or more and 6.5 ⁇ L or less).
  • the amount of non-aqueous electrolyte per 1 mAh of discharge capacity may be 3.5 ⁇ L or more, or 4.0 ⁇ L or more.
  • It represents the time rate.
  • the current value I (mA) at the t hour rate is expressed as C/t.
  • the rated capacity of the lithium secondary battery varies depending on the battery size.
  • the discharge capacity is preferably the initial discharge capacity.
  • the initial discharge capacity is, for example, the discharge capacity when a battery after break-in charge and discharge is charged and discharged under the above conditions. It may be the discharge capacity when the battery is charged and discharged under the conditions of .
  • the discharge capacity when charged and discharged under the above conditions at the time of initial use can be considered to correspond to the initial discharge capacity.
  • the outer diameter R may be 3 mm or more and 6.5 mm or less, and the height H may be 15 mm or more and 65 mm or less.
  • the outer diameter R may be between 3 mm and 5.5 mm.
  • the height H may be between 15 and 45 mm.
  • the outer diameter R of the lithium secondary battery is the maximum outer diameter of the battery case in the battery (the battery after assembly).
  • the height H of the battery is the height of the assembled battery, and is the distance from the bottom surface of the battery (outer bottom surface of the battery case) to the top surface of the battery (top surface of the sealing member).
  • a cylindrical lithium secondary battery having a small outer diameter R as described above is hereinafter also referred to as a "pin-shaped battery".
  • a pin-shaped battery has a limited capacity in the battery case, but it also needs to accommodate an electrode group with sufficient capacity, so the amount of non-aqueous electrolyte that can be accommodated is limited.
  • the rated capacity of lithium secondary batteries is derived from the deposition and dissolution of lithium metal, it is possible to increase the capacity. is relatively easy.
  • the lithium metal does not impregnate the non-aqueous electrolyte, it is possible to impregnate the positive electrode with a larger amount of the non-aqueous electrolyte. Therefore, it is considered that the effect of suppressing the decrease in capacity due to the increase in the amount of the non-aqueous electrolyte appears greatly.
  • the reaction between the non-aqueous electrolyte and the highly active lithium metal is suppressed even in the event of an abnormality, making it possible to sufficiently ensure safety.
  • a general carbonate ester is used as a solvent for the non-aqueous electrolyte, even if the amount of the non-aqueous electrolyte per 1 mAh discharge capacity is less than 2.5 ⁇ L, the reaction between the non-aqueous electrolyte and lithium metal can be suppressed. It is difficult.
  • Such a remarkable difference in safety due to the difference in solvents is particularly remarkable in pin type batteries having a small volume in the battery case.
  • the ratio of the non-aqueous electrolyte to the volume of the battery case is relatively large compared to batteries of general size, so it is believed that the solvent has a strong impact on safety. .
  • the filling rate in the battery is, for example, 71% or more, preferably 72% or more.
  • the filling rate is 95% or less, preferably 93% or less, and preferably 90% or less from the viewpoint of easily ensuring higher charge-discharge cycle characteristics. These lower and upper limits can be combined arbitrarily.
  • the filling factor is, for example, 71-95%, and may be 71-93% or 72-93%. When the filling rate is 95% or less, expansion and contraction of the electrode during charging and discharging are not greatly restricted, and favorable cycle characteristics are likely to be obtained.
  • the filling rate means the ratio (volume %) of the solid and liquid components contained in the battery case to the volume of the battery case.
  • the sum of the ratio (% by volume) of the remaining space to the volume in the battery case and the filling rate (% by volume) is 100% by volume.
  • Solid and liquid components include, for example, electrodes (ie, electrodes and separators), non-aqueous electrolytes, leads, insulating rings disposed between the sealing member and the electrodes, and the like.
  • the volume of solid components such as leads and insulating rings can be calculated from the size of the solid components.
  • the volume of solid components such as electrodes and separators can be calculated based on the mass of the solid components and the specific gravity of the materials that make up the solid components.
  • the volume of a liquid component such as a non-aqueous electrolyte can be determined by taking it out of the battery and weighing it.
  • the filling rate is preferably the initial filling rate.
  • the initial filling rate is, for example, the filling rate when the battery after break-in charging and discharging is charged and discharged under the above conditions. may be For example, for commercially available lithium secondary batteries, the filling rate before first use can be considered to correspond to the initial filling rate.
  • the negative electrode has at least a negative electrode current collector.
  • Lithium metal is deposited on the surface of the negative electrode by charging. More specifically, lithium ions contained in the non-aqueous electrolyte receive electrons on the negative electrode during charging to become lithium metal, which is deposited on the surface of the negative electrode. Lithium metal deposited on the surface of the negative electrode dissolves as lithium ions in the non-aqueous electrolyte due to discharge.
  • the lithium ions contained in the non-aqueous electrolyte may be derived from the lithium salt added to the non-aqueous electrolyte, or may be supplied from the positive electrode active material during charging. There may be.
  • the negative electrode may include a negative electrode current collector and a sheet-like lithium metal or lithium alloy that adheres to the surface of the negative electrode current collector. That is, a base layer containing lithium metal may be provided in advance on the negative electrode current collector. Lithium alloys may contain elements other than lithium, such as aluminum, magnesium, indium, and zinc. By providing a base layer containing lithium metal and depositing lithium metal thereon during charging, dendrite-like deposition can be suppressed.
  • the thickness of the underlying layer containing lithium metal is not particularly limited, but may be, for example, in the range of 5 ⁇ m to 25 ⁇ m.
  • the negative electrode may include a lithium ion storage layer (a layer that expresses capacity by absorbing and releasing lithium ions by the negative electrode active material (graphite, etc.)) supported by the negative electrode current collector.
  • the open circuit potential of the negative electrode at full charge may be 70 mV or less with respect to lithium metal (dissolution deposition potential of lithium).
  • the open circuit potential of the negative electrode at full charge is 70 mV or less with respect to lithium metal, lithium metal exists on the surface of the lithium ion storage layer at full charge.
  • the lithium ion storage layer is formed by layering a negative electrode mixture containing a negative electrode active material.
  • the negative electrode mixture may contain a binder, a thickener, a conductive material, etc., in addition to the negative electrode active material.
  • Examples of negative electrode active materials include carbonaceous materials, Si-containing materials, and Sn-containing materials.
  • the negative electrode may contain one type of negative electrode active material, or may contain two or more types in combination.
  • Examples of carbonaceous materials include graphite, graphitizable carbon (soft carbon), and non-graphitizable carbon (hard carbon).
  • the conductive material is, for example, a carbon material.
  • carbon materials include carbon black, acetylene black, ketjen black, carbon nanotubes, and graphite.
  • binders include fluorine resins, polyacrylonitrile, polyimide resins, acrylic resins, polyolefin resins, and rubber-like polymers.
  • fluororesins include polytetrafluoroethylene and polyvinylidene fluoride.
  • the negative electrode current collector may be a conductive sheet.
  • a foil, a film, or the like is used as the conductive sheet.
  • the material of the negative electrode current collector may be any conductive material other than lithium metal and lithium alloy.
  • the conductive material may be a metallic material such as a metal, an alloy, or the like.
  • the conductive material is preferably a material that does not react with lithium. More specifically, materials that form neither alloys nor intermetallic compounds with lithium are preferred.
  • Such conductive materials include, for example, copper (Cu), nickel (Ni), iron (Fe), alloys containing these metal elements, or graphite in which the basal plane is preferentially exposed.
  • alloys include copper alloys and stainless steel (SUS). Among them, copper and/or copper alloys having high electrical conductivity are preferred.
  • the thickness of the negative electrode current collector is not particularly limited, and is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the positive electrode includes, for example, a positive electrode current collector and a positive electrode mixture layer supported by the positive electrode current collector.
  • the positive electrode mixture layer includes, for example, a positive electrode active material, a conductive material, and a binder.
  • the positive electrode mixture layer may be formed only on one side of the positive electrode current collector, or may be formed on both sides.
  • the positive electrode is obtained, for example, by applying a positive electrode mixture slurry containing a positive electrode active material, a conductive material, and a binder on both sides of a positive electrode current collector, drying the coating film, and then rolling.
  • a positive electrode active material is a material that absorbs and releases lithium ions.
  • positive electrode active materials include lithium-containing transition metal oxides, transition metal fluorides, polyanions, fluorinated polyanions, and transition metal sulfides. Among them, lithium-containing transition metal oxides are preferable in terms of low production cost and high average discharge voltage.
  • the lithium contained in the lithium-containing transition metal oxide is released from the positive electrode as lithium ions during charging and deposited as lithium metal on the negative electrode or the negative electrode current collector. During discharge, lithium metal is dissolved from the negative electrode to release lithium ions, which are occluded by the composite oxide of the positive electrode. Lithium ions involved in charging and discharging are generally derived from the solute in the non-aqueous electrolyte and the positive electrode active material.
  • the transition metal elements contained in the lithium-containing transition metal oxide include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, W, and the like.
  • the lithium-containing transition metal oxide may contain one or more transition metal elements.
  • the transition metal elements may be Co, Ni and/or Mn.
  • the lithium-containing transition metal oxide may contain one or more main group elements as needed. Typical elements include Mg, Al, Ca, Zn, Ga, Ge, Sn, Sb, Pb, and Bi. A typical element may be Al or the like.
  • a composite oxide containing Ni as a transition metal element, Co and/or Mn, and Al as an optional component, and having a layered structure and a rock salt crystal structure provides a high capacity.
  • the molar ratio of the total amount mLi of lithium possessed by the positive electrode and the negative electrode to the amount mM of the metal M other than lithium possessed by the positive electrode: mLi/mM may be set to, for example, 2.0 or less. good.
  • the binder conductive material, etc., for example, those exemplified for the negative electrode can be used.
  • the shape and thickness of the positive electrode current collector can be selected from the shape and range of the positive electrode current collector.
  • Examples of materials for the positive electrode current collector (conductive sheet) include metal materials containing Al, Ti, Fe, and the like.
  • the metal material may be Al, Al alloy, Ti, Ti alloy, Fe alloy, or the like.
  • the Fe alloy may be stainless steel (SUS).
  • the thickness of the positive electrode current collector is not particularly limited, and is, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • separators used in lithium secondary batteries and lithium ion secondary batteries can be used without particular limitations.
  • Such separators are porous sheets that are ion-permeable and insulating.
  • porous sheets include porous membranes, woven fabrics, non-woven fabrics, and the like.
  • the porous membranes may be uniaxially or biaxially oriented sheets and the like.
  • the material of the porous sheet is not particularly limited, but may be a polymeric material.
  • polymeric materials include polyolefin resins, polyamide resins, polyimide resins, cellulose, and the like.
  • polyolefin resins include polyethylene, polypropylene and copolymers of ethylene and propylene.
  • the porous sheet may contain one material or two or more materials.
  • the porous sheet may contain additives as needed. An inorganic filler etc. are mentioned as an additive.
  • the thickness of the separator is not particularly limited, and can be appropriately selected from a range of, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • the thickness of the porous membrane is, for example, 5 ⁇ m or more and 50 ⁇ m or less.
  • the separator may have a heat-resistant layer on at least one surface layer. That is, the separator may include a substrate and a heat-resistant layer. The heat-resistant layer is formed on at least one main surface selected from two main surfaces of the substrate. The heat-resistant layer has insulating properties.
  • the thickness of the heat-resistant layer may be 3% to 50% of the thickness of the separator.
  • the total of them may be 3% to 50% of the thickness of the separator.
  • the heat-resistant layer can suppress shrinkage of the base material when the temperature of the electrode group rises excessively.
  • the base material shrinks, short-circuiting between the positive electrode and the negative electrode is more likely to occur, and the temperature of the electrode group is more likely to rise.
  • shrinkage of the base material can be suppressed, so that further temperature rise of the electrode group can be suppressed.
  • the base material may be the porous sheet described above, that is, the separator used in lithium secondary batteries or lithium ion secondary batteries.
  • the substrate may be, for example, a porous membrane containing polyolefin resin. Polyolefin resin is desirable in that it has excellent durability and has a function of closing pores when the temperature rises to a certain level (that is, a shutdown function).
  • the substrate may have a single-layer structure, a two-layer structure, or a three-layer or more structure.
  • the heat-resistant layer may contain inorganic particles (or inorganic fillers) and polymers (or macromolecules or resins).
  • the polymer binds the inorganic particles to the substrate.
  • As the polymer it is desirable to use a heat-resistant resin having higher heat resistance than the main component of the substrate.
  • the heat-resistant layer may contain inorganic particles as a main component (for example, 80% by mass or more), or may contain a heat-resistant resin as a main component (for example, 40% by mass or more).
  • the heat-resistant layer may contain no inorganic particles and may contain a heat-resistant resin.
  • Polyamide resin, polyimide resin, polyamide-imide resin, etc. may be used as the heat-resistant resin. Above all, it preferably contains at least one selected from the group consisting of aromatic polyamides, aromatic polyimides and aromatic polyamideimides. These are known as polymers with particularly high heat resistance. From the viewpoint of heat resistance, aramids, that is, meta-aramids (meta-based wholly aromatic polyamides) and para-aramids (para-based wholly aromatic polyamides) are preferred.
  • Inorganic particles are particles composed of insulating inorganic compounds.
  • examples of inorganic particle materials include oxides, oxide hydrates, hydroxides, nitrides, carbides, sulfides, etc., which may contain metallic elements.
  • at least one selected from the group consisting of aluminum oxide, boehmite, talc, titanium oxide, and magnesium oxide is preferable from the viewpoint of insulation and heat resistance.
  • the inorganic particles may include lithium-containing phosphates.
  • the lithium-containing phosphate is at least one selected from the group consisting of lithium phosphate (Li 3 PO 4 ), dilithium hydrogen phosphate (Li 2 HPO 4 ) and lithium dihydrogen phosphate (LiH 2 PO 4 ). There may be. Among these, lithium phosphate is preferable because it is highly effective in suppressing heat generation of the battery in the event of an abnormality.
  • the average particle size of the inorganic particles is not particularly limited, but may be, for example, 0.2 ⁇ m to 2 ⁇ m.
  • the average particle size of the lithium-containing phosphate may be from 0.1 ⁇ m to 1.0 ⁇ m, or from 0.1 ⁇ m to 0.5 ⁇ m. By setting the average particle size to 0.1 ⁇ m or more, it is possible to ensure sufficient pores necessary for the penetration of the non-aqueous electrolyte. By setting the average particle size to 1.0 ⁇ m or less, a heat-resistant layer in which the lithium-containing phosphate is densely packed can be formed.
  • the ratio of the lithium-containing phosphate is desirably 20% by mass or more, and may be 50% by mass or more.
  • the second layer may contain only inorganic particles other than the lithium-containing phosphate, may contain 60% by mass or more of the inorganic particles other than the lithium-containing phosphate, or may contain only the heat-resistant resin.
  • the non-aqueous electrolyte may be any non-aqueous electrolyte having lithium ion conductivity, and contains a solvent and an electrolyte salt dissolved in the solvent.
  • a solvent contains an ether compound as a main component.
  • the electrolyte salt contains at least a lithium salt. Lithium ions and anions are generated by dissolving the lithium salt in the solvent.
  • the non-aqueous electrolyte may be liquid, or may be gelled by a polymer that absorbs a solvent.
  • solvents include ester compounds, nitrile compounds, amide compounds, and halogen-substituted compounds thereof, in addition to ether compounds.
  • the non-aqueous electrolyte may contain one of these non-aqueous solvents, or two or more of them. Fluoride etc. are mentioned as a halogen substitution body.
  • ester compounds include carbonic acid esters and carboxylic acid esters.
  • Cyclic carbonates include ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC), and the like.
  • Chain carbonic acid esters include dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and the like.
  • Cyclic carboxylic acid esters include ⁇ -butyrolactone, ⁇ -valerolactone and the like. Examples of chain carboxylic acid esters include ethyl acetate, methyl propionate, and methyl fluoropropionate.
  • Ether compounds include cyclic ethers and chain ethers, among which general formula (1): R1-( OCH2CH2 ) n - OR2 (In formula (1), R1 and R2 are each independently an alkyl group having 1 to 5 carbon atoms, and n is 1 to 3.)
  • the lowest unoccupied molecular orbital (LUMO) of non-fluorinated ethers exists at a high energy level. Therefore, the non-fluorinated ether is less likely to be reductively decomposed even when it comes into contact with lithium metal, which has a strong reducing power. Furthermore, since oxygen in the non-fluorinated ether skeleton strongly interacts with lithium ions, the lithium salt contained as an electrolyte salt in the non-aqueous electrolyte can be easily dissolved.
  • a non-fluorinated ether is suitable as a solvent for the non-aqueous electrolyte of a lithium secondary battery in that it suppresses the side reaction between the lithium metal and the non-aqueous electrolyte and increases the solubility of the lithium salt in the solvent.
  • first ether compound non-fluorinated ether
  • first ether compound include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether. , diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and the like.
  • a 1st ether compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the ether compound may contain a fluorinated ether.
  • the interaction of oxygen in the ether skeleton of fluorinated ethers with lithium ions is reduced compared to non-fluorinated ethers. This is thought to be due to the strong electronegativity of the fluorine atom, which attracts the electrons of the entire molecule toward the inner core, lowering the orbital level of the lone pair of oxygen electrons in the ether skeleton, which should interact with the lithium ion. be done.
  • a fluorinated ether and a non-fluorinated ether may be used together.
  • the charging/discharging reaction proceeds more uniformly in the lithium secondary battery. This is probably because the solvation energies of the ether compound and lithium ions are well balanced.
  • the fluorination rate of the second ether compound may be 60% or more.
  • the fluorination rate of the second ether compound is the number ratio of fluorine atoms to the total number of fluorine atoms and hydrogen atoms contained in the second ether compound, expressed in percentage (%).
  • the second ether compound fluorinated ether
  • fluorinated ether examples include 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether and the like.
  • a 2nd ether compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the ratio of the total amount of the first ether compound and the second ether compound to the entire solvent may be 80% by volume or more.
  • the ratio of the total amount is 80% by volume or more, the effect of improving the cycle characteristics of the lithium secondary battery becomes more pronounced.
  • the volume ratio of the volume V1 of the first ether compound to the volume V2 of the second ether compound: V1/V2 is preferably from 1/0.5 to 1/4, more preferably from 1/0.5 to 1/ 2.
  • anions that are used in non-aqueous electrolytes of lithium secondary batteries can be used. Specific examples include BF 4 ⁇ , ClO 4 ⁇ , PF 6 ⁇ , CF 3 SO 3 ⁇ , CF 3 CO 2 ⁇ , imide anions, oxalate complex anions, and the like.
  • the electrolyte salt may contain at least one selected from the group consisting of imide anions, PF 6 - and oxalate complex anions.
  • the oxalate complex anion tends to precipitate lithium metal uniformly in the form of fine particles due to its interaction with lithium.
  • bis(fluorosulfonyl)imide anion (N(SO 2 F) 2 ⁇ ) is preferred. Therefore, the lithium salt preferably contains lithium bis(fluorosulfonyl)imide (hereinafter also referred to as “LiFSI”).
  • oxalate complex anions examples include bisoxalate borate anions, difluorooxalate borate anions (BF 2 (C 2 O 4 ) ⁇ ), PF 4 (C 2 O 4 ) ⁇ , PF 2 (C 2 O 4 ) 2 ⁇ and the like. is mentioned. Among them, difluorooxalate borate anion (BF 2 (C 2 O 4 ) ⁇ ) is preferred. Therefore, the lithium salt preferably contains lithium difluorooxalate borate (hereinafter also referred to as “LiFOB”).
  • LiFOB lithium difluorooxalate borate
  • the electrolyte salt preferably contains at least one selected from the group consisting of LiPF 6 , imide salts and oxalate complex salts.
  • the concentration of the lithium salt in the non-aqueous electrolyte is, for example, 0.5 mol/L or more and 3.5 mol/L or less.
  • the concentration of the oxalate complex salt in the non-aqueous electrolyte may be 0.05 mol/L or more and 1 mol/L or less.
  • lithium secondary battery of the present embodiment An example of the lithium secondary battery of the present embodiment will be specifically described below with reference to the drawings.
  • the components described above can be applied to the components of the example lithium secondary battery described below.
  • the components of the example described below can be modified based on the above description.
  • the matters described below may be applied to the above embodiments.
  • components that are not essential for the lithium secondary battery according to the present disclosure may be omitted. It should be noted that in the following figures, the scale of the constituent elements has been changed to facilitate understanding.
  • FIG. 1 is a schematic longitudinal sectional view of a pin-shaped cylindrical lithium secondary battery according to one embodiment of the present invention.
  • a cylindrical secondary battery 100 includes a bottomed cylindrical battery case 20 having an opening, a wound electrode group 10 and a non-aqueous electrolyte (not shown) housed in the battery case 20, and the battery case 20. and a sealing member 40 for sealing the opening.
  • the electrode group 10 is composed of a positive electrode 11, a negative electrode 12, and a separator 13 interposed therebetween.
  • the sealing member 40 is hat-shaped and has a ring-shaped brim (brim 40a) and cylindrical terminal portions 40b and 40c protruding from the inner circumference of the brim 40a in the thickness direction.
  • a ring-shaped insulating gasket 30 is arranged on the periphery of the sealing member 40 so as to cover the brim 40a.
  • the battery case 20 is insulated from the sealing member 40 and the battery case 20 is sealed by bending the open end of the battery case 20 inward through the gasket 30 and crimping the peripheral edge of the sealing member 40 . be done.
  • a space is formed between the upper end surface (top surface) of the electrode group 10 and the bottom surface of the sealing member 40 .
  • a first insulating ring 50A is arranged in this space to restrict contact between the electrode group 10 and the sealing member 40 .
  • a donut-shaped second insulating ring 50B made of an electrically insulating material is arranged so as to cover the outer surface of the bent open end of the battery case 20 and the surface of the gasket 30 around it.
  • One end of the positive electrode current collecting lead 60 is connected to the positive electrode 11 by welding or the like, and the other end is connected to the bottom surface of the sealing member 40 by welding or the like through a hole formed in the center of the first insulating ring 50A. ing. That is, the positive electrode 11 and the sealing member 40 are electrically connected via the positive electrode current collecting lead 60, and the sealing member 40 functions as an external positive electrode terminal.
  • a negative electrode current collecting lead 70 is connected to the outermost negative electrode 12 of the electrode group 10 by welding or the like.
  • the other end of the negative electrode current collecting lead 70 is connected to the inner wall of the battery case 20 at a welding point 70a. That is, the negative electrode 12 and the battery case 20 are electrically connected via the negative electrode current collecting lead 70, and the battery case 20 functions as an external negative electrode terminal.
  • the welding point 70 a is formed, for example, on the inner wall on the opening side of the battery case 20 with respect to the upper end surface of the electrode group 10 .
  • cylindrical lithium secondary batteries as shown in FIG. 1 were produced.
  • the cylindrical lithium secondary battery had an outer diameter R of 4 mm and a height H of 25 mm.
  • the filling rate was within the range of 75% to 90%.
  • Example 1 Lithium-containing transition metal oxide containing Li, Ni, Co and Al (the molar ratio of Li to the total of Ni, Co and Al is 1.0) and having a layered structure and a rock salt crystal structure.
  • NCA positive electrode active material 100 parts by mass, 4 parts by mass of acetylene black as a conductive material, 4 parts by mass of polyvinylidene fluoride (PVdF) as a binder, and N-methyl-2-pyrrolidone (NMP) as a dispersion medium.
  • a positive electrode slurry was prepared by adding and mixing.
  • the positive electrode slurry is applied to both sides of an aluminum foil (thickness 15 ⁇ m) as a positive electrode current collector, dried, and then compressed in the thickness direction to form a positive electrode 11 (thickness: 80 ⁇ m).
  • the positive electrode 11 was provided with an exposed portion of the positive electrode current collector in the width direction of the positive electrode (direction parallel to the winding axis of the electrode group) during fabrication, and a ribbon-shaped aluminum positive electrode current collecting lead 60 (width 1.0 mm) was provided. 0 mm, thickness 0.05 mm) was connected to the exposed portion.
  • a negative electrode 12 (50 ⁇ m thick) was prepared by attaching a 20 ⁇ m thick lithium metal foil to both surfaces of a copper foil (10 ⁇ m thick) as a negative electrode current collector. An exposed portion of the negative electrode current collector was provided at a portion corresponding to the outermost periphery of the negative electrode 12 in the electrode group 10, and one end portion of a ribbon-shaped nickel negative electrode current collecting lead 70 (width 1.5 mm, thickness 0.05 mm) was provided. was connected to the exposed part.
  • Electrode Group 10 The positive electrode 11 and the negative electrode 12 were wound with the separator 13 interposed therebetween to form the wound electrode group 10 .
  • the electrode group 10 was fixed by attaching a fixing insulating tape to the winding end.
  • a polyethylene porous film having a thickness of 16 ⁇ m was used as the separator.
  • the electrode group 10 obtained in (3) above is inserted into a bottomed cylindrical battery case 20 having an opening formed of a nickel-plated iron plate, and the negative electrode collector is The other end of the electrical lead 70 was welded to the inner wall of the battery case 20 at a welding point 70a.
  • the welding point 70a is formed by placing the first insulating ring 50A on the electrode group 10, passing the other end of the positive electrode current collecting lead 60 pulled out from the electrode group 10 through a hole in the first insulating ring 50A, and applying nickel plating. It was connected to the bottom surface of a sealing member 40 made of iron.
  • a ring-shaped insulating gasket 30 is attached to the periphery of the sealing member 40 .
  • Example 2 Particles of aluminum oxide (Al 2 O 3 ), particles of lithium phosphate (Li 3 PO 4 ), and aromatic polyamide were added to the surface layer of the positive electrode side of the polyethylene porous film as the separator in a mass ratio of 48:48. 2 was formed (thickness: 2 ⁇ m).
  • a cylindrical lithium secondary battery (battery A2) was produced in the same manner as in Example 1, except that a separator having such a heat-resistant layer was used.
  • Example 3 A cylindrical lithium secondary battery (battery A3) was produced.
  • Example 4 A cylindrical lithium secondary battery (battery A4) was produced.
  • a non-aqueous electrolyte (electrolyte B) was prepared by dissolving LiPF 6 in a mixed solvent containing ethylene carbonate (EC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC) at a mass ratio of 20:20:60. prepared. At this time, the concentration of LiPF 6 in the non-aqueous electrolyte was set to 1.0 mol/L.
  • a cylindrical lithium secondary battery (battery B1) was produced in the same manner as in Example 1, except that 2.5 ⁇ L of electrolyte B per 1 mAh discharge capacity was injected into the battery case instead of electrolyte A.
  • Capacity retention rate After charging at a constant current of 0.1 It until the closed circuit voltage of the battery reached 4.2 V, the battery was charged at a constant voltage of 4.2 V until the current reached 0.05 It. After that, the battery was rested for 20 minutes and discharged at a constant current of 0.1 It until the closed circuit voltage of the battery reached 2.5V. This cycle was repeated for 100 cycles. The ratio (%) of the discharge capacity at the 100th cycle to the discharge capacity at the 1st cycle was determined as the capacity retention rate.
  • batteries A1 to A4 in which the solvent contains an ether compound as a main component and the amount of non-aqueous electrolyte per 1 mAh of discharge capacity is 2.5 ⁇ L or more and 6.5 ⁇ L or less are all excellent capacities. showed the maintenance rate. In addition, regardless of the presence or absence of the heat-resistant layer of the separator, it showed high safety in the nail penetration test. On the other hand, Battery B3, in which the amount of non-aqueous electrolyte per 1 mAh of discharge capacity was less than 2.5 ⁇ L, had an insufficient capacity retention rate. In addition, both batteries B1 and B2, in which the solvent mainly contains a carbonate ester, have a low capacity retention rate, and even battery B1 with an injection amount of 2.5 ⁇ L can ensure sufficient safety in a nail penetration test. It was difficult.
  • the present disclosure is suitable for cylindrical lithium secondary batteries (especially pin-shaped secondary batteries), and as power sources for various portable electronic devices that require small power sources, such as glasses (3D glasses, etc.), hearing aids, stylus pens, and wearable terminals. It can be used preferably. While the invention has been described in terms of presently preferred embodiments, such disclosure is not to be construed in a limiting sense. Various alterations and modifications will no doubt become apparent to those skilled in the art to which the invention pertains after reading the above disclosure. Therefore, the appended claims are to be interpreted as covering all variations and modifications without departing from the true spirit and scope of the invention.

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PCT/JP2023/006877 2022-02-28 2023-02-24 円筒形リチウム二次電池 Ceased WO2023163135A1 (ja)

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WO2025070647A1 (ja) * 2023-09-29 2025-04-03 パナソニックＩｐマネジメント株式会社 非水電解質二次電池

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JP2007220455A (ja) 2006-02-16 2007-08-30 Matsushita Electric Ind Co Ltd 非水電解液二次電池
WO2014132660A1 (ja) * 2013-03-01 2014-09-04 パナソニック株式会社 リチウムイオン二次電池
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WO2025070647A1 (ja) * 2023-09-29 2025-04-03 パナソニックＩｐマネジメント株式会社 非水電解質二次電池

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