WO2024219289A1 - 非水電解質二次電池および非水電解質二次電池用のセパレータ - Google Patents

非水電解質二次電池および非水電解質二次電池用のセパレータ Download PDF

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Publication number
WO2024219289A1
WO2024219289A1 PCT/JP2024/014396 JP2024014396W WO2024219289A1 WO 2024219289 A1 WO2024219289 A1 WO 2024219289A1 JP 2024014396 W JP2024014396 W JP 2024014396W WO 2024219289 A1 WO2024219289 A1 WO 2024219289A1
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Prior art keywords
separator
secondary battery
negative electrode
spacer
layer
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PCT/JP2024/014396
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English (en)
French (fr)
Japanese (ja)
Inventor
和寿 宇津宮
翔 浦田
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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 EP24792564.7A priority Critical patent/EP4700964A1/en
Priority to CN202480025785.XA priority patent/CN121100444A/zh
Priority to JP2025515180A priority patent/JPWO2024219289A1/ja
Publication of WO2024219289A1 publication Critical patent/WO2024219289A1/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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure relates to non-aqueous electrolyte secondary batteries and separators for non-aqueous electrolyte secondary batteries.
  • Lithium secondary batteries (lithium metal secondary batteries) are known as one type of non-aqueous electrolyte secondary battery.
  • lithium metal is precipitated on the negative electrode during charging, and the lithium metal dissolves in the non-aqueous electrolyte during discharging.
  • Various proposals have been made for lithium secondary batteries.
  • Patent document 1 JP Patent Publication 2020-077497A describes in claim 1, "A separator for use in a non-aqueous electrolyte battery, the separator comprising a substrate and a convex pattern provided on at least one surface of the substrate, the pattern including end regions disposed at both ends of the surface direction of the convex shape and a central region disposed between the opposing end regions, the end regions having an apex protruding in a thickness direction perpendicular to the surface direction and disposed at the boundary with the central region, and the central region having a recessed portion having a thickness smaller than that of the apex.”
  • One of the objectives of this disclosure is to provide a non-aqueous electrolyte secondary battery with high cycle characteristics.
  • the non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
  • the negative electrode is an electrode in which a metal containing at least one selected from the group consisting of lithium and sodium is precipitated during charging and the metal dissolves during discharging.
  • the separator includes a substrate and a spacer formed on the substrate, and the spacer includes a protrusion and a skirt disposed on the outer edge of the protrusion and thinner than the protrusion.
  • the separator is for a non-aqueous electrolyte secondary battery and includes a substrate and a spacer formed on the substrate, the spacer including a protrusion and a bottom portion that is disposed on the outer edge of the protrusion and is thinner than the protrusion.
  • FIG. 1A is a top view diagrammatically illustrating an example of the separator of the first embodiment.
  • FIG. 1B is a cross-sectional view that diagrammatically illustrates a portion of the separator shown in FIG. 1A.
  • FIG. 2 is a top view diagrammatically illustrating another example of the separator of the first embodiment.
  • FIG. 3 is a top view diagrammatically illustrating another example of the separator of the first embodiment.
  • FIG. 4A is a cross-sectional view that illustrates an example of a manufacturing process for the separator of embodiment 1.
  • FIG. 4B is a cross-sectional view that illustrates an example of a step subsequent to the step of FIG. 4A.
  • FIG. 5 is a vertical cross-sectional view illustrating an example of a nonaqueous electrolyte secondary battery according to the second embodiment.
  • FIG. 6 is a cross-sectional view showing a schematic view of a part of the lithium secondary battery shown in FIG.
  • nonaqueous electrolyte secondary battery (Nonaqueous electrolyte secondary battery)
  • the nonaqueous electrolyte secondary battery according to this embodiment may be referred to as a “nonaqueous electrolyte secondary battery (B)” or a “secondary battery (B)”.
  • the secondary battery (B) is The battery includes a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and a non-aqueous electrolyte.
  • the negative electrode deposits a metal containing at least one selected from the group consisting of lithium and sodium during charging.
  • the separator includes a substrate and a spacer formed on the substrate.
  • the spacer includes a protrusion and a spacer disposed on the outer edge of the protrusion. The spacer is spaced apart from the protrusion. and a thin skirt.
  • separators with spacers may deteriorate.
  • a negative electrode in which metal (negative electrode active material) precipitates and dissolves during charging and discharging the separator deforms with charging and discharging.
  • the separator has a substrate and a spacer formed on the substrate, the force applied to the substrate at the corner of the lower end of the spacer increases when the separator deforms. As a result, the substrate in contact with the corner becomes thinner, making it more likely for micro-short circuits to occur. Micro-short circuits lead to a deterioration in battery characteristics (e.g., cycle characteristics).
  • the inventors of the present application have newly discovered that by using a spacer with a bottom portion, it is possible to suppress deterioration of the substrate caused by the spacer.
  • the present disclosure is based on this new finding.
  • the metal that precipitates during charging may contain lithium.
  • the metal that precipitates during charging may be lithium metal.
  • the lithium metal may contain trace amounts of other metal elements, or may be a lithium alloy.
  • a lithium secondary battery in which lithium metal is deposited on the negative electrode during charging is also called a lithium metal secondary battery.
  • the negative electrode of a lithium secondary battery lithium metal is deposited during charging, and the lithium metal dissolves during discharging.
  • the negative electrode has at least a negative electrode current collector, and lithium metal is deposited on the negative electrode current collector.
  • the lithium secondary battery which is a secondary battery (B)
  • LB lithium secondary battery
  • a lithium secondary battery for example, 70% or more of the rated capacity is realized by the deposition and dissolution of lithium metal.
  • the movement of electrons at the negative electrode during charging and discharging is mainly due to the deposition and dissolution of lithium metal at the negative electrode.
  • 70 to 100% (for example, 80 to 100% or 90 to 100%) of the movement of electrons (current from another perspective) at the negative electrode during charging and discharging is due to the deposition and dissolution of lithium metal.
  • the negative electrode of a lithium secondary battery (LB) is different from a negative electrode in which the movement of electrons at the negative electrode during charging and discharging is mainly due to the absorption and release of lithium ions by the negative electrode active material (such as graphite).
  • the hem is formed so as to connect to the outer edge of the convex portion. It is preferable that the hem is formed on almost the entire outer edge of the convex portion. For example, if the convex portion is a linear convex portion, it is preferable that the hem is formed on both sides of the linear convex portion in the width direction. If the convex portion is a dot-shaped convex portion, it is preferable that the hem is formed on the entire outer periphery of the dot-shaped convex portion. It is preferable that the hem is located on 70% or more, 80% or more, 90% or more, or 95% or more of the outer edge of the convex portion.
  • the width Wf of the bottom portion may be 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more, and may be 40 ⁇ m or less, or 20 ⁇ m or less.
  • the width Wf of the bottom portion may be in the range of 1 ⁇ m to 40 ⁇ m (e.g., in the range of 5 ⁇ m to 20 ⁇ m).
  • the width Wc of the convex portion may be 100 ⁇ m or more, or 500 ⁇ m or more, and may be 5000 ⁇ m or less, or 1000 ⁇ m or less.
  • the width Wc of the convex portion may be in the range of 100 ⁇ m to 5000 ⁇ m (e.g., in the range of 500 ⁇ m to 1000 ⁇ m).
  • the ratio Wf/Wc of the width Wf of the bottom to the width Wc of the convex portion may be 0.001 or more, 0.006 or more, 0.02 or more, or 0.08 or more.
  • the ratio Wf/Wc may be 0.6 or less, 0.4 or less, 0.12 or less, or 0.08 or less.
  • the ratio Wf/Wc may be in the range of 0.001 to 0.4 (e.g., 0.006 to 0.12 or 0.006 to 0.08).
  • the average height Hf of the hem may be 0.5 ⁇ m or more, 1 ⁇ m or more, or 2 ⁇ m or more, and may be 10 ⁇ m or less, or 5 ⁇ m or less.
  • the average height Hf of the hem may be in the range of 0.5 ⁇ m to 10 ⁇ m (e.g., in the range of 1 ⁇ m to 5 ⁇ m).
  • the average height Hc of the convex portions may be 10 ⁇ m or more, or 20 ⁇ m or more, or may be 100 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, or 30 ⁇ m or less.
  • the height of the convex portions may be approximately constant throughout the separator so that the gap between the plates formed by the spacers is approximately constant.
  • the ratio Hf/Hc of the average height Hf of the bottom to the average height Hc of the convex portions may be 0.005 or more, 0.01 or more, or 0.05 or more, and may be 0.25 or less, or 0.15 or less.
  • the ratio Hf/Hc may be in the range of 0.005 to 0.25 (e.g., in the range of 0.01 to 0.15).
  • the average height of the hem at one point can be found from an image of the cross section of the hem. Specifically, the cross-sectional area of the hem and the length of the base of the hem are measured from the image, and the average height of one point of the hem can be found by dividing the cross-sectional area by the length of the base.
  • the average height of the hem Hf can be found by finding the average height of each of 20 or more (for example, 20) arbitrarily selected cross-sectional images of the hem, and then taking the arithmetic mean of the average heights obtained for the 20 or more points.
  • the height of a single convex portion can be found by measuring the height of the highest part of the convex portion in the cross-sectional image of the spacer.
  • the average height Hc of the convex portions is found by finding the height of each convex portion from the cross-sectional images of 20 or more arbitrarily selected convex portions (e.g., 20 locations) and then taking the arithmetic average of the heights obtained at the 20 or more locations.
  • the bottom may become thinner as it moves away from the protrusion. This configuration can particularly prevent damage to the base material caused by the corners of the protrusion.
  • the bottom may be formed with a substantially constant thickness.
  • the ratio Sa/Ss of the area Ss of the spacer to the area Sa of the main surface on which the spacer is formed, out of the two main surfaces of the separator substrate may be 0.001 or more, or 0.01 or more, and may be 0.25 or less, 0.10 or less, or 0.05 or less. By making the ratio Sa/Ss 0.25 or less, it is possible to reduce the disadvantage caused by the area occupied by the spacer becoming too large.
  • the material of the protrusions and the material of the bottom part may be different or the same. By making the material of the protrusions and the bottom part the same, the adhesion between the bottom part and the protrusions can be improved.
  • the protrusions and the bottom part may contain the same resin.
  • the protrusions and the bottom part may contain the same resin and the same filler.
  • the method for producing the secondary battery (B) is not particularly limited.
  • the secondary battery (B) may be produced by a method similar to a known production method.
  • the secondary battery (B) can be produced by enclosing an electrode group including a positive electrode, a negative electrode, and a separator, and a non-aqueous electrolyte in an exterior body.
  • the separator according to this embodiment may be referred to as a "separator (S)" below.
  • the separator (S) is a separator for a non-aqueous electrolyte secondary battery.
  • the separator (S) includes a substrate and a spacer formed on the substrate, and the spacer includes a protrusion and a skirt portion that is disposed on the outer edge of the protrusion and is thinner than the protrusion.
  • the separator (S) may be the same as that described for the separator of the secondary battery (B).
  • the matters described for the separator of the secondary battery (B) may be applied to the separator (S), so duplicated explanations may be omitted.
  • the separator (S) may be used as the separator of the secondary battery (B).
  • the matters described for the separator (S) may be applied to the separator of the secondary battery (B).
  • the spacer may include a resin (e.g., an insulating resin), or may include a resin and a filler.
  • the spacer may be made of only a resin, or may be made of a resin and a filler.
  • resin materials include fluorine-containing resins (polyvinylidene fluoride (PVdF), polytetrafluoroethylene, etc.), fluorine-containing rubbers (vinylidene fluoride-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, etc.), rubbers (styrene-butadiene copolymer or its hydrogenated product, acrylonitrile-butadiene copolymer or its hydrogenated product, methacrylate-acrylate copolymer, styrene-acrylate copolymer, acrylonitrile-acrylate copolymer, ethylene propylene rubber, polyvinyl alcohol, polyvinyl acetate, etc.), cellulose derivatives, These include polymers (ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, etc.), acrylic resins (acrylic acid-methacrylic acid copolymers, etc.),
  • the resin content Cr in the spacer may be 10 volume % or more, 30 volume % or more, 40 volume % or more, or 50 volume % or more, or 100 volume % or less, 90 volume % or less, 80 volume % or less, or 60 volume % or less.
  • the filler contained in the spacer is not particularly limited.
  • the filler may be an insulating filler.
  • the filler may be an inorganic filler, an organic filler, or a mixture thereof.
  • filler materials include oxides, nitrides, carbides, etc.
  • oxides include aluminum oxide (alumina), magnesium oxide, titanium oxide, zirconium oxide, silicon oxide, etc.
  • nitrides include silicon nitride, aluminum nitride, titanium nitride, etc.
  • Examples of carbides include silicon carbide, etc.
  • the shape of the filler may be spherical or may be a shape other than spherical.
  • the average particle size of the filler is not particularly limited, but may be 0.1 ⁇ m or more or 0.5 ⁇ m or more, and may be 10 ⁇ m or less, 5 ⁇ m or less, or 2 ⁇ m or less.
  • the average particle size can be measured by the following method. First, the cross section of the spacer is photographed with an electron microscope to obtain an image of the cross section. Next, the image is subjected to image processing such as binarization to identify the particle portion.
  • the diameter of a circle having the same area as the cross section area of each particle (circle equivalent diameter) is obtained, and the arithmetic mean of the obtained circle equivalent diameters can be used as the average particle size.
  • the arithmetic mean can be obtained from, for example, 20 particles.
  • the average particle size of other particles contained in the electrode plate and separator can also be obtained by a similar method.
  • the spacer may be formed on the main surface on the positive electrode side of the two main surfaces of the substrate, or on the main surface on the negative electrode side.
  • the spacer is formed on the main surface on the positive electrode side of the substrate, the substrate is significantly deformed due to precipitation of metal (negative electrode active material) during charging. Therefore, the technology disclosed herein is particularly preferably used when the spacer is formed on the main surface on the positive electrode side of the substrate.
  • the shape of the convex portion included in the spacer is not particularly limited as long as it can form a space in at least one of the above-mentioned regions.
  • the convex portion may include at least one type selected from the group consisting of linear convex portions and dot-shaped convex portions.
  • the spacer may include linear protrusions arranged in a mesh pattern.
  • the mesh pattern may be a pattern that combines polygons (triangles, squares, hexagons, etc.).
  • the mesh pattern may be a honeycomb pattern.
  • the spacer may include a plurality of linear protrusions arranged in a stripe pattern.
  • the spacer may include a plurality of dot-shaped protrusions regularly arranged at regular intervals.
  • the shape of the cross section of the linear protrusion is not particularly limited.
  • the cross section may be rectangular, trapezoidal, or semicircular.
  • the spacer may have a non-porous structure that is impermeable to ions of the metal (e.g., lithium ions) that is the negative electrode active material.
  • ions of the metal e.g., lithium ions
  • Such a spacer can be realized by forming the spacer under conditions that do not make it porous.
  • a spacer having a non-porous structure may be formed by printing the constituent material of the spacer as ink on a separator.
  • “lithium ions do not permeate” means that an amount that affects the characteristics and shape of the battery does not permeate, and includes the case where an amount of lithium ions that can be considered to be substantially not permeating moves within the spacer.
  • the substrate is a sheet that can be used as a separator for a non-aqueous electrolyte secondary battery.
  • the substrate may be composed of only a substrate layer.
  • the substrate may include a substrate layer and a composite material layer formed on the substrate layer.
  • the composite material layer contains a polymer and inorganic particles.
  • the separator may be disposed so that the composite material layer faces the positive electrode, or the composite material layer faces the negative electrode.
  • the spacer may be formed on the substrate layer or on the composite material layer. By forming a spacer on the composite material layer, the effect of suppressing the thermal shrinkage of the substrate layer is particularly enhanced.
  • the positive electrode and the negative electrode are more likely to short-circuit, which makes the temperature of the electrode group more likely to rise.
  • laminating a composite material layer on the base material layer it is possible to suppress the shrinkage of the base material layer when the temperature of the electrode group rises. As a result, it is possible to suppress further temperature increases in the electrode group.
  • the substrate layer is made of a porous sheet having ion permeability and insulation properties.
  • porous sheets include porous membranes, woven fabrics, and nonwoven fabrics.
  • the material of the separator is not particularly limited, but may be a polymeric material.
  • polymeric materials include polyolefin resins, polyamide resins, and cellulose.
  • polyolefin resins include polyethylene, polypropylene, and copolymers of ethylene and propylene.
  • the substrate layer may contain additives as necessary. Examples of additives include inorganic fillers.
  • the substrate layer may be made of a sheet used as a separator in a nonaqueous electrolyte secondary battery (e.g., a lithium secondary battery).
  • the composite layer includes a polymer (hereinafter sometimes referred to as "polymer (PL)”) and inorganic particles.
  • the inorganic particles may include first particles and/or second particles.
  • the first particles are particles of a phosphate containing lithium.
  • the second particles are particles other than the first particles.
  • the composite layer is a layer that allows lithium ions to pass through.
  • the phosphate constituting the first particles may be 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 ).
  • lithium phosphate is preferred because of its high effect of suppressing heat generation in the battery under abnormal conditions.
  • a preferred example of the second particles is a particle made of an insulating inorganic compound that does not melt or decompose when the battery generates abnormal heat.
  • the second particles may be inorganic particles that are generally used as inorganic fillers. Examples of materials for the second particles include aluminum oxide, boehmite, talc, titanium oxide, magnesium oxide, and silicon oxide.
  • the polymer (PL) is preferably a polymer having higher heat resistance than the main component of the separator's base layer.
  • the polymer (PL) may contain at least one selected from the group consisting of aromatic polyamide, aromatic polyimide, and aromatic polyamideimide. These are known as polymers with high heat resistance. Aramid (fully aromatic polyamide) is preferred from the viewpoint of heat resistance.
  • the inorganic particles may include the above-mentioned first particles and second particles other than phosphate.
  • the composite material layer may include a first layer including the first particles and a second layer including the second particles. This configuration can particularly enhance the effect of suppressing excessive temperature rise in the electrode group. Note that the composite material layer may be composed of only the first layer or only the second layer.
  • the first layer and the second layer may be laminated on the main surface on the positive electrode side of the two main surfaces of the substrate layer, or on the main surface on the negative electrode side, or on different main surfaces.
  • the separator and the spacer may have a laminate structure of substrate layer/first layer/second layer/spacer, substrate layer/second layer/first layer/spacer, first layer/second layer/substrate layer/spacer, or second layer/first layer/substrate layer/spacer.
  • the first layer and the second layer may be disposed on different main surfaces of the substrate layer.
  • the separator and the spacer may have a laminate structure of first layer/substrate layer/second layer/spacer, or second layer/substrate layer/first layer/spacer.
  • the thickness of the substrate is not particularly limited and may be 5 ⁇ m or more, or 10 ⁇ m or more, and 50 ⁇ m or less, or 40 ⁇ m or less.
  • the substrate layer may be 5 ⁇ m or more, or 10 ⁇ m or more, and 50 ⁇ m or less, or 40 ⁇ m or less.
  • the separator (S) can be manufactured by forming a spacer on a substrate.
  • the method of forming the spacer is not particularly limited.
  • the bottom portion and the protrusion may be formed simultaneously or separately. As described below, the bottom portion and the protrusion may be formed integrally.
  • the bottom and protrusions may be formed by applying a coating liquid and then drying it.
  • the coating liquid can be prepared by mixing the components of each part with a liquid medium (dispersion medium).
  • liquid medium include organic solvents (such as N-methyl-2-pyrrolidone).
  • the coating liquid may be applied using a dispenser or other known printing methods such as gravure printing, inkjet printing, and screen printing. Drying may be performed by known methods such as drying by heating or natural drying.
  • step (i) An example of a method for forming a spacer is described below.
  • This method includes steps (i) and (ii).
  • step (i) a first layer that will become the bottom of the convex portion and the hem is formed on the substrate.
  • step (ii) a second layer that will become the part of the convex portion other than the bottom of the convex portion is formed on the first layer.
  • the first and second layers can be formed, for example, by applying a coating liquid to the substrate and then drying it.
  • the substrate may be prepared by the following method. First, a substrate layer is prepared. A commercially available substrate layer may be used. Next, a composite material layer is formed on the substrate layer.
  • a coating liquid is formed by mixing the components of the composite material layer with a liquid medium (dispersion medium).
  • a liquid medium dispersion medium
  • the coating liquid is applied to the substrate layer to form a coating film, and the coating film is then dried.
  • the composite material layer can be formed.
  • liquid medium used to form the coating liquid. Examples of such liquid media include organic solvents (such as N-methyl-2-pyrrolidone).
  • the coating liquid may be applied by known methods such as a method using a bar coater.
  • drying may be performed by known methods such as drying by heating or natural drying.
  • the components described below are merely examples, and the components of the secondary battery (B) of this embodiment are not limited to the components described below. Known components may be used for components other than those characteristic of the secondary battery (B) of this embodiment.
  • the secondary battery (B) is a lithium secondary battery (lithium secondary battery (LB))
  • LB lithium secondary battery
  • the secondary battery (B) is a battery other than a lithium secondary battery
  • components appropriate for that battery positive electrode, negative electrode, non-aqueous electrolyte, etc.
  • the separator and spacer have been described above, so duplicated description will be omitted.
  • the shape of the secondary battery (B) is not particularly limited. Examples of shapes of the secondary battery (B) include a cylindrical shape, a coin shape, a rectangular shape, a sheet shape, a flat shape, etc.
  • the negative electrode is disposed so as to face the positive electrode.
  • the separator is disposed between the positive electrode and the negative electrode.
  • the positive electrode, the negative electrode, and the separator may be wound so that the separator is disposed between the positive electrode and the negative electrode.
  • a wound type electrode group a strip-shaped positive electrode, a strip-shaped negative electrode, and a strip-shaped separator are used.
  • the positive electrode, the negative electrode, and the separator may be stacked.
  • a flat positive electrode, a flat negative electrode, and a flat separator may be stacked. That is, the electrode group may be a wound type electrode group or a stacked type electrode group.
  • the negative electrode includes a negative electrode current collector.
  • a lithium secondary battery LB
  • lithium metal is deposited on the negative electrode current collector by charging. More specifically, lithium ions contained in the non-aqueous electrolyte receive electrons on the negative electrode current collector by charging, becoming lithium metal, and depositing on the negative electrode current collector.
  • the lithium metal deposited on the negative electrode current collector is dissolved as lithium ions in the non-aqueous electrolyte by discharging.
  • the lithium ions contained in the non-aqueous electrolyte may be derived from a lithium salt added to the non-aqueous electrolyte, may be supplied from a positive electrode active material by charging, or may be both of these.
  • a conductive sheet can be used for the negative electrode current collector. If the electrode group is of a wound type, a strip-shaped conductive sheet is used. Examples of conductive sheets include conductive films and metal foils.
  • 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 metal.
  • the conductive material is preferably a material that does not react with lithium.
  • the conductive material is preferably one that does not form an alloy or an intermetallic compound with lithium. Examples of such conductive materials include copper (Cu), nickel (Ni), iron (Fe), and alloys containing these metal elements, or graphite with the basal surface preferentially exposed. Examples of alloys include copper alloys and stainless steel (SUS).
  • the conductive material is preferably copper and/or a copper alloy.
  • the thickness of the negative electrode current collector is not particularly limited and may be in the range of 5 to 300 ⁇ m.
  • a negative electrode mixture layer may be formed on the surface of the negative electrode current collector.
  • the negative electrode mixture layer is formed, for example, by applying a paste containing a negative electrode active material such as graphite to at least a portion of the surface of the negative electrode current collector.
  • the thickness of the negative electrode mixture layer is set to be sufficiently thin so that lithium metal can be precipitated in the negative electrode.
  • the negative electrode may include a negative electrode current collector and a sheet-like lithium metal or lithium alloy disposed on the negative electrode current collector. That is, the negative electrode current collector may be provided with a base layer (a layer of lithium metal or lithium alloy) containing lithium metal in advance.
  • the lithium alloy may contain elements such as aluminum, magnesium, indium, and zinc in addition to lithium.
  • the positive electrode may include a positive electrode current collector and a positive electrode mixture layer supported by the positive electrode current collector.
  • the positive electrode mixture layer includes a positive electrode active material.
  • the positive electrode mixture layer may include a positive electrode active material, a conductive material, and a binder.
  • the positive electrode mixture layer may be formed on only one side of the positive electrode current collector, or may be formed on both sides.
  • the positive electrode can be formed, for example, by applying a positive electrode mixture slurry including a positive electrode active material, a conductive material, and a binder to the positive electrode current collector, drying the coating, and then rolling.
  • the 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, transition metal sulfides, etc. Among these, lithium-containing transition metal oxides are preferred because of their low manufacturing costs and high average discharge voltage.
  • 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, etc.
  • the lithium-containing transition metal oxide may contain one type of transition metal element, or may contain two or more types.
  • the transition metal element may be Co, Ni, and/or Mn.
  • the lithium-containing transition metal oxide may contain one or more typical elements as necessary.
  • the typical elements include Mg, Al, Ca, Zn, Ga, Ge, Sn, Sb, Pb, Bi, etc.
  • the typical element may be Al, etc.
  • the conductive material is, for example, a carbon material.
  • carbon materials include carbon black (acetylene black, ketjen black, etc.), carbon nanotubes, and graphite.
  • Binders include, for example, fluororesins, polyacrylonitrile, polyimide resins, acrylic resins, polyolefin resins, rubber-like polymers, etc.
  • Fluororesins include polytetrafluoroethylene, polyvinylidene fluoride, etc.
  • the positive electrode current collector may be a conductive sheet.
  • conductive sheets include foils and films.
  • the surface of the positive electrode current collector may be coated with a carbon material.
  • the material of the positive electrode current collector may be, for example, a metal material containing Al, Ti, Fe, etc.
  • the metal material may be Al, an Al alloy, Ti, a Ti alloy, an Fe alloy, etc.
  • the Fe alloy may be stainless steel (SUS).
  • the thickness of the positive electrode current collector is not particularly limited and may be in the range of 5 to 300 ⁇ m.
  • Non-aqueous electrolyte The non-aqueous electrolyte having lithium ion conductivity contains, for example, a non-aqueous solvent, and lithium ions and anions dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte may be in a liquid state or a gel state.
  • a liquid non-aqueous electrolyte is prepared by dissolving a lithium salt in a non-aqueous solvent. When the lithium salt dissolves in the non-aqueous solvent, lithium ions and anions are produced.
  • the gelled non-aqueous electrolyte contains a lithium salt and a matrix polymer, or a lithium salt, a non-aqueous solvent, and a matrix polymer.
  • a matrix polymer for example, a polymer material that absorbs the non-aqueous solvent and gels is used. Examples of the polymer material include fluororesin, acrylic resin, polyether resin, etc.
  • the anion of the oxalate complex may contain boron and/or phosphorus.
  • Examples of the anion of the oxalate complex include bisoxalate borate anion, BF 2 (C 2 O 4 ) ⁇ , PF 4 (C 2 O 4 ) ⁇ , PF 2 (C 2 O 4 ) 2 ⁇ , etc.
  • the non-aqueous electrolyte may contain these anions alone or in combination of two or more kinds.
  • the non-aqueous electrolyte preferably contains an anion of an oxalate complex.
  • the interaction between the anion of the oxalate complex and lithium makes it easier for the lithium metal to be precipitated uniformly in the form of fine particles. This makes it easier to suppress localized precipitation of the lithium metal.
  • the anion of the oxalate complex may be combined with another anion.
  • the other anion may be an anion of PF 6 - and/or an imide.
  • the non-aqueous electrolyte may contain LiBF 2 (C 2 O 4 ) (lithium difluorooxalatoborate) as a solute (lithium salt).
  • non-aqueous solvents examples include esters, ethers, nitriles, amides, and halogen-substituted derivatives thereof.
  • the non-aqueous electrolyte may contain one or more of these non-aqueous solvents.
  • halogen-substituted derivatives include fluorides.
  • Esters include, for example, carbonate esters and carboxylate esters.
  • Cyclic carbonate esters include ethylene carbonate, propylene carbonate, fluoroethylene carbonate (FEC), etc.
  • Chain carbonate esters include dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate, etc.
  • Cyclic carboxylate esters include ⁇ -butyrolactone, ⁇ -valerolactone, etc.
  • Chain carboxylate esters include ethyl acetate, methyl propionate, methyl fluoropropionate, etc.
  • Ethers include cyclic ethers and chain ethers.
  • cyclic ethers include 1,3-dioxolane, 4-methyl-1,3-dioxolane, tetrahydrofuran, and 2-methyltetrahydrofuran.
  • chain ethers include 1,2-dimethoxyethane, diethyl ether, ethyl vinyl ether, methyl phenyl ether, benzyl ethyl ether, diphenyl ether, dibenzyl ether, 1,2-diethoxyethane, and diethylene glycol dimethyl ether.
  • 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 anion in the non-aqueous electrolyte may be 0.5 mol/L or more and 3.5 mol/L or less.
  • the concentration of the anion of the oxalate complex in the non-aqueous electrolyte may be 0.05 mol/L or more and 1 mol/L or less.
  • the non-aqueous electrolyte may contain an additive.
  • the additive may form a coating on the negative electrode.
  • the coating derived from the additive is formed on the negative electrode, which makes it easier to suppress the formation of dendrites.
  • examples of such additives include vinylene carbonate, FEC, vinyl ethyl carbonate (VEC), etc.
  • the secondary battery (B) usually includes an exterior body that houses an electrode group and a non-aqueous electrolyte.
  • the exterior body is not particularly limited, and any known exterior body can be used.
  • FIG. 1A A top view of a separator 50 of the first embodiment is shown in FIG. 1A.
  • the separator 50 includes a substrate 51 and a spacer 52 formed on the substrate 51.
  • FIG. 1B A cross-sectional view of the separator 50 in a portion where the spacer 52 exists is shown in FIG. 1B.
  • FIG. 1B hatching of the spacer 52 is omitted in FIG. 1B.
  • the cross section of FIG. 1B is a cross-sectional view in a direction perpendicular to the direction in which the linear convex portion 52a extends. As shown in FIG.
  • the spacer 52 includes a linear convex portion 52a and two skirt portions 52b arranged on both sides of the convex portion 52a.
  • the spacer 52 (linear convex portion 52a) is formed in a honeycomb pattern as shown in FIG. 1A.
  • FIG. 1B shows the height Hx of the convex portion 52a, the width Wc of the convex portion 52a, and the width Wf of one skirt portion 52b.
  • the hem 52b is connected to the outer edge of the convex portion 52a and is thinner than the convex portion 52a.
  • the hem 52b has a tapered shape that becomes thinner the further away from the convex portion 52a.
  • the angle ⁇ between the surface 52bs of the hem 52b and the surface 51s of the substrate 51 is smaller than the angle ⁇ between the side surface 52as of the convex portion 52a and the surface 51s of the substrate 51.
  • the inflection point 52p where the angle between the surface of the spacer 52 and the surface 51s of the substrate 51 changes significantly, can be regarded as the boundary between the convex portion 52a and the hem 52b. If there is no clear inflection point 52p, the region where the angle ⁇ is 45° or less can be regarded as the region of the hem 52b, and the other region can be regarded as the region of the convex portion 52a.
  • FIG. 2 Another example of the arrangement of the spacers 52 (protrusions 52a) is shown in Figures 2 and 3.
  • a plurality of linear spacers 52 spaced apart from each other are formed on the substrate 51.
  • a plurality of linear spacers 52 arranged in a stripe pattern are formed on the substrate 51.
  • a first coating liquid is prepared by dispersing the material (resin, filler, etc.) that will mainly become the bottom portion 52b in a liquid medium (dispersion medium).
  • the liquid medium is not particularly limited, and an organic solvent (N-methyl-2-pyrrolidone, etc.) may be used.
  • the first coating liquid is thinly applied to the area where the convex portion 52a and bottom portion 52b are to be formed and dried to form a first layer 52x on the substrate 51 as shown in FIG. 4A.
  • the shape of the bottom portion 52b can be changed by changing the concentration of the first coating liquid, etc. For example, it is possible to make the bottom portion 52b more likely to have a tapered shape by diluting the first coating liquid.
  • the second coating liquid is prepared by dispersing the material (resin, filler, etc.) that will mainly become the convex portion 52a in a liquid medium (dispersion medium).
  • the liquid medium is not particularly limited, and an organic solvent (N-methyl-2-pyrrolidone, etc.) may be used.
  • the second coating liquid is applied thickly to the area where the convex portion 52a is to be formed and dried to form the second layer 52y on the first layer 52x, as shown in FIG. 4B. In this manner, the spacer 52 is formed.
  • the portion of the first layer 52x that is directly below the second layer 52y and the second layer 52y constitute the convex portion 52a.
  • the portion of the first layer 52x that is not directly below the second layer 52y constitutes the bottom portion 52b.
  • the coating liquid may be applied using a dispenser or a known printing method such as gravure printing, inkjet printing, or screen printing.
  • the coating liquid may be dried using a known method such as drying by heating or natural drying.
  • Fig. 5 is a longitudinal sectional view showing a nonaqueous electrolyte secondary battery according to the second embodiment. Note that in Fig. 5, the spacer and the space formed by the spacer are omitted.
  • the cylindrical secondary battery (nonaqueous electrolyte secondary battery) 10 shown in FIG. 5 includes a cylindrical battery case, and a wound electrode group 14 and a nonaqueous electrolyte (not shown) housed within the battery case.
  • the battery case includes a case body 15, which is a cylindrical metal container with a bottom, and a sealing body 16 that seals the opening of the case body 15.
  • a gasket 27 is disposed between the case body 15 and the sealing body 16. The gasket 27 ensures that the battery case is airtight.
  • insulating plates 17 and 18 are disposed at both ends of the electrode group 14 in the winding axis direction.
  • the case body 15 has a step 21 formed, for example, by partially pressing the side wall of the case body 15 from the outside.
  • the step 21 may be formed in an annular shape along the circumferential direction of the case body 15 on the side wall of the case body 15.
  • the sealing body 16 is supported by the surface of the step 21 on the opening side.
  • the sealing body 16 includes a filter 22, a lower valve body 23, an insulating member 24, an upper valve body 25, and a cap 26. In the sealing body 16, these members are stacked in this order. Each of the above members constituting the sealing body 16 is, for example, disk-shaped or ring-shaped.
  • the lower valve body 23 and the upper valve body 25 are connected to each other at their respective centers, and the insulating member 24 is interposed between their respective peripheral edges.
  • the filter 22 and the lower valve body 23 are connected to each other at their respective peripheral edges.
  • the upper valve body 25 and the cap 26 are connected to each other at their respective peripheral edges. In other words, each member except the insulating member 24 is electrically connected to each other.
  • the lower valve body 23 has an air vent (not shown). Therefore, when the internal pressure of the battery case rises due to abnormal heat generation or the like, the upper valve body 25 bulges toward the cap 26 and separates from the lower valve body 23. This cuts off the electrical connection between the lower valve body 23 and the upper valve body 25. If the internal pressure rises further, the upper valve body 25 breaks and gas is discharged from the opening formed in the cap 26.
  • FIG. 6 is an enlarged view of a portion of the electrode group 14.
  • FIG. 6 includes a portion near the positive electrode surrounded by region II in FIG. 5 and a portion near the negative electrode surrounded by region III in FIG. 5.
  • the electrode group 14 includes a positive electrode 11, a negative electrode 12, and a separator 50.
  • the positive electrode 11, the negative electrode 12, and the separator 50 are all strip-shaped.
  • the separator 50 is the separator described in embodiment 1.
  • the electrode group 14 is formed by winding the positive electrode 11, the negative electrode 12, and the separator 50 so that the separator 50 is disposed between the positive electrode 11 and the negative electrode 12.
  • the positive electrode 11 includes a positive electrode current collector 11a and a positive electrode composite layer 11b.
  • the positive electrode current collector 11a is electrically connected to a cap 26, which functions as a positive electrode terminal, via a positive electrode lead 19.
  • the negative electrode 12 is shown as a negative electrode (negative electrode current collector) in a state in which lithium metal is not deposited.
  • the negative electrode 12 is electrically connected to a case body 15, which functions as a negative electrode terminal, via a negative electrode lead 20.
  • the spacer 52 is formed on one of the two main surfaces of the substrate 51, the main surface on the positive electrode 11 side, but it may also be formed on the main surface on the negative electrode 12 side.
  • the spacer 52 forms a space 14s between the positive electrode 11 and the negative electrode 12.
  • lithium metal is precipitated on the negative electrode 12 during charging.
  • the substrate 51 in the portion without the protrusion 52a moves toward the space 14s. Because there is a space 14s between the positive electrode 11 and the negative electrode 12, the volume change of the electrode group 14 accompanying the precipitation of lithium metal is reduced, improving the cycle characteristics.
  • the spacer 52 has a bottom portion 52b, so damage to the substrate 51 by the spacer 52 can be suppressed.
  • a non-aqueous electrolyte secondary battery A positive electrode and A negative electrode; a separator disposed between the positive electrode and the negative electrode; and a non-aqueous electrolyte, the negative electrode is an anode in which a metal containing at least one selected from the group consisting of lithium and sodium is deposited during charging and in which the metal is dissolved during discharging;
  • the separator includes a substrate and a spacer formed on the substrate, the spacer includes a protrusion and a skirt portion disposed on an outer edge of the protrusion and thinner than the protrusion.
  • (Technique 6) 6.
  • (Technique 7) A separator for a non-aqueous electrolyte secondary battery, A substrate and a spacer formed on the substrate, The spacer includes a protrusion and a bottom portion that is disposed on an outer edge of the protrusion and is thinner than the protrusion.
  • the secondary battery (B) according to this embodiment will be specifically described below based on examples.
  • a number of lithium secondary batteries having different separators were fabricated and evaluated.
  • separator SA1 Preparation of separator SA1 First, a strip-shaped porous polyethylene film (average thickness 10 ⁇ m) was prepared as a substrate layer. Next, a porous composite material layer (average thickness 2 ⁇ m) was formed on one side of the substrate layer. The composite material layer was formed by forming the second layer and the first layer in this order on the substrate layer.
  • the second layer was formed as follows. First, N-methyl-2-pyrrolidone (NMP) and calcium chloride were mixed in a mass ratio of 94.2:5.8. The mixture was heated to about 80°C to completely dissolve the calcium chloride. Then, the solution was returned to room temperature, and 2200 g was collected, and 0.6 mol of paraphenylenediamine (PPD) was added to completely dissolve the solution. While the solution was kept at about 20°C, 0.6 mol of terephthalic acid dichloride (TPC) was added little by little. The resulting solution was aged at about 20°C for 1 hour to obtain a polymerization liquid.
  • NMP N-methyl-2-pyrrolidone
  • PPD paraphenylenediamine
  • TPC terephthalic acid dichloride
  • this polymerization liquid was mixed with an N-methyl-2-pyrrolidone solution in which 5.8 mass% of calcium chloride was dissolved, and a solution (coating liquid) in which the concentration of paraphenylene terephthalamide (PPTA), an aromatic polyamide (aramid), was 2 mass% was obtained.
  • PPTA paraphenylene terephthalamide
  • aramid aromatic polyamide
  • the coating liquid was then applied onto the substrate layer using a slot die method to form a coating film.
  • the substrate layer on which the coating film was formed was then left to stand for 1 hour in an atmosphere at a temperature of 25°C and a relative humidity of 70% to precipitate the aromatic polyamide.
  • the NMP and calcium chloride in the coating film were then removed by rinsing with water.
  • the coating film was then dried at 60°C for 5 minutes to form a second layer.
  • the first layer was formed as follows. First, lithium phosphate (Li 3 PO 4 ) particles and poly N-vinylacetamide (PNVA) were mixed in a mass ratio of 100:8 to obtain a mixture. The lithium phosphate particles used had a volume-based median diameter of 0.19 ⁇ m. Water (ion-exchanged water) was added to the obtained mixture and stirred to prepare a slurry (coating liquid) with a solid content concentration of 12 mass%. Next, the slurry was coated on the second layer by microgravure coating to form a coating film. Next, the coating film was dried in a drying oven attached to the coater. In this way, the first layer was formed. In this way, a composite material layer was formed.
  • lithium phosphate (Li 3 PO 4 ) particles and poly N-vinylacetamide (PNVA) were mixed in a mass ratio of 100:8 to obtain a mixture.
  • the lithium phosphate particles used had a volume-based median diameter of 0.19 ⁇ m.
  • Water
  • spacers were formed on the composite material layer in a honeycomb pattern as shown in FIG. 3. Specifically, first, a first layer 52x was formed on the composite material layer as shown in FIG. 4A. Next, a second layer 52y was formed on the first layer 52x as shown in FIG. 4B. At this time, each layer was formed so that the average height Hc of the convex portions, the average height Hf of the bottom portion, and the ratio Wf/Wc of the bottom width Wf to the convex width Wc were the values shown in Table 1. The width Wc of the convex portions was set to 500 ⁇ m. The first layer 52x and the second layer 52y were formed using a coating liquid containing resin and alumina particles (inorganic filler). In this manner, a separator SA1 having spacers was formed.
  • Separators SA2 to SA4 were produced in the same manner and under the same conditions as separator SA1, except that the spacers were formed so that the ratio Wf/Wc was the value shown in Table 1. At this time, the width Wc of the convex portion was set to 500 ⁇ m, the same as separator SA1.
  • Separator SC1 was produced in the same manner and under the same conditions as separator SA1, except that a spacer was formed that was composed only of the convex portion and did not include a bottom portion.
  • a lithium secondary battery A1 was produced in the following manner.
  • NCA rock salt type lithium-containing transition metal oxide
  • AB conductive material
  • PVdF polyvinylidene fluoride
  • NMP N-methyl-2-pyrrolidone
  • the obtained positive electrode mixture slurry was applied to both sides of a strip-shaped Al foil (positive electrode current collector) and then dried to form a coating film of the positive electrode mixture.
  • the coating film was rolled using a roller.
  • the resulting laminate of the positive electrode current collector and the positive electrode composite material was cut into a predetermined electrode size, thus producing a positive electrode including a positive electrode current collector and positive electrode composite material layers disposed on both sides of the positive electrode current collector.
  • Negative Electrode A negative electrode was used in which a layer of rolled lithium metal (thickness 25 ⁇ m) was provided on both sides of a strip of copper foil (thickness 12 ⁇ m).
  • LiPF6 and LiBF2 ( C2O4 ) were dissolved in the resulting mixed solvent to a concentration of 1 mol/L and a concentration of 0.1 mol/L, respectively, to prepare a liquid non-aqueous electrolyte.
  • Batteries A2 to A4 and C1 were produced under the same conditions and by the same method as those for producing battery A1, except that separators SA2 to SA4 or separator SC1 were used instead of separator SA1.
  • a charge/discharge test was conducted on each battery prepared as described above.
  • the battery was charged under the following conditions in a thermostatic chamber at 25°C, then left for 20 minutes and discharged under the following conditions.
  • the battery was charged at a constant current of 2.15 mA per unit area (cm 2 ) of the electrode until the battery voltage reached 4.1 V, and then charged at a constant voltage of 4.1 V until the current value per unit area of the electrode reached 0.54 mA.
  • Capacity retention rate 100 x C (200) / C (1)
  • the spacer formation conditions and the evaluation results of the separator and battery are shown in Table 1.
  • the air permeability resistance (Gurley seconds) in Table 1 is a relative value when the value of separator SC1 is set to 100%. The higher the air permeability resistance value, the lower the separator's breathability. The higher the capacity retention rate, the better the cycle characteristics.
  • Batteries A1 to A4 are secondary batteries (B) according to the present disclosure, and battery C1 is a comparative example battery.
  • the capacity retention rates of batteries A1 to A4 were higher than that of battery C1. This is believed to be the effect of forming a hem. There was a tendency for the capacity retention rate to decrease as the value of Wf/Wc increased. This is believed to be because the breathability of the separator decreases as the value of Wf/Wc increases.

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PCT/JP2024/014396 2023-04-20 2024-04-09 非水電解質二次電池および非水電解質二次電池用のセパレータ Ceased WO2024219289A1 (ja)

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CN202480025785.XA CN121100444A (zh) 2023-04-20 2024-04-09 非水电解质二次电池及非水电解质二次电池用的分隔件
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Citations (3)

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Publication number Priority date Publication date Assignee Title
JP2013137984A (ja) * 2011-09-05 2013-07-11 Sony Corp セパレータおよび非水電解質電池
JP2020077497A (ja) 2018-11-06 2020-05-21 旭化成株式会社 微細パタンを有するセパレータ、捲回体および非水電解質電池
WO2022224872A1 (ja) * 2021-04-20 2022-10-27 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013137984A (ja) * 2011-09-05 2013-07-11 Sony Corp セパレータおよび非水電解質電池
JP2020077497A (ja) 2018-11-06 2020-05-21 旭化成株式会社 微細パタンを有するセパレータ、捲回体および非水電解質電池
WO2022224872A1 (ja) * 2021-04-20 2022-10-27 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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