WO2022009734A1 - Élément de stockage d'énergie à électrolyte non aqueux - Google Patents

Élément de stockage d'énergie à électrolyte non aqueux Download PDF

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WO2022009734A1
WO2022009734A1 PCT/JP2021/024557 JP2021024557W WO2022009734A1 WO 2022009734 A1 WO2022009734 A1 WO 2022009734A1 JP 2021024557 W JP2021024557 W JP 2021024557W WO 2022009734 A1 WO2022009734 A1 WO 2022009734A1
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separator layer
negative electrode
active material
aqueous electrolyte
layer
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PCT/JP2021/024557
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English (en)
Japanese (ja)
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直樹 上原
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株式会社Ｇｓユアサ
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Publication of WO2022009734A1 publication Critical patent/WO2022009734A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/449—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
    • 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
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • 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
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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

  • the present invention relates to a non-aqueous electrolyte power storage element.
  • Non-aqueous electrolyte secondary batteries represented by lithium-ion non-aqueous electrolyte secondary batteries are widely used in personal computers, electronic devices such as communication terminals, automobiles, etc. due to their high energy density.
  • the non-aqueous electrolyte secondary battery generally includes an electrode body having a pair of electrodes electrically separated by a separator, and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the two electrodes. It is configured to charge and discharge by doing.
  • capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as power storage elements other than non-aqueous electrolyte secondary batteries.
  • Patent Document 1 describes a technique for improving the charge acceptability of a lithium ion secondary battery by combining a non-aqueous electrolytic solution containing a specific compound with a negative electrode active material containing a specific lithium storage alloy and an element. Proposed.
  • the non-aqueous electrolyte storage element using acrylic resin as the binder of the negative electrode active material layer containing the negative electrode active material has higher charge acceptance performance than the non-aqueous electrolyte storage element using styrene-butadiene rubber as the binder.
  • the non-aqueous electrolyte power storage element using acrylic resin as the binder of the negative electrode active material layer tends to increase the resistance after the charge / discharge cycle.
  • the present invention has been made based on the above circumstances, and a non-aqueous electrolyte power storage element capable of suppressing an increase in resistance after a charge / discharge cycle even when an acrylic resin is used as a binder for the negative electrode active material layer.
  • the purpose is to provide.
  • the non-aqueous electrolyte power storage element includes a negative electrode having a negative electrode active material layer containing an acrylic resin, a positive electrode, a first separator layer, and a second separator layer.
  • the layer is interposed between the negative electrode and the positive electrode, the second separator layer is interposed between the negative electrode and the first separator layer, and the porosity of the second separator layer is higher than that of the first separator layer.
  • the non-aqueous electrolyte power storage element according to one aspect of the present invention can suppress an increase in resistance after a charge / discharge cycle even when an acrylic resin is used as the binder of the negative electrode active material layer.
  • the non-aqueous electrolyte power storage element includes a negative electrode having a negative electrode active material layer containing an acrylic resin, a positive electrode, a first separator layer, and a second separator layer.
  • the layer is interposed between the negative electrode and the positive electrode, the second separator layer is interposed between the negative electrode and the first separator layer, and the porosity of the second separator layer is higher than that of the first separator layer.
  • the non-aqueous electrolyte power storage element using acrylic resin as the binder of the negative electrode active material layer is superior in charge acceptability as compared with the non-aqueous electrolyte power storage element using styrene-butadiene rubber as the binder, but it is filled.
  • the resistance after the discharge cycle tends to increase.
  • the non-aqueous electrolyte power storage element includes a first separator layer interposed between the negative electrode and the positive electrode, and a second separator layer interposed between the negative electrode and the first separator layer having a higher porosity than the first separator layer. It is possible to suppress an increase in resistance after a charge / discharge cycle. The reason for this is not clear, but it can be thought of as follows.
  • the acrylic resin When acrylic resin is used as the binder for the negative electrode active material layer, the acrylic resin has a high swelling rate with respect to the non-aqueous electrolyte, so that the binder swells due to the non-aqueous electrolyte as the charge / discharge cycle progresses, and the negative electrode active material layer expands. It's easy to do. Therefore, when a separator having a low pore ratio is opposed to the negative electrode active material layer using acrylic resin as the binder, the negative electrode active material layer expands and invades the pores of the separator, and the pores of the separator are clogged. By causing this, it is considered that the resistance of the non-aqueous electrolyte power storage element is significantly increased.
  • the non-aqueous electrolyte power storage element has a second separator layer having a high porosity facing the negative electrode active material layer using an acrylic resin as a binder, so that the pores of the first separator layer having a low porosity can be obtained. It is possible to suppress the invasion of the negative electrode active material layer and prevent the occurrence of clogging of the first separator layer. As a result, it is considered that the effect of suppressing the increase in resistance of the non-aqueous electrolyte power storage element after the charge / discharge cycle is improved. Therefore, the non-aqueous electrolyte power storage element can suppress an increase in resistance after the charge / discharge cycle while taking advantage of the characteristics of the acrylic resin having high charge acceptance performance.
  • the "porosity" is a volume-based value, and is calculated from the mass per unit area, the thickness, and the true density of the constituent materials.
  • the first separator layer contains a synthetic resin as a main component and the second separator layer contains inorganic particles. Since the first separator layer contains a synthetic resin as a main component and the second separator layer contains inorganic particles, the effect of suppressing the invasion of the negative electrode active material layer into the pores of the first separator layer can be enhanced. , The effect of suppressing the increase in resistance of the non-aqueous electrolyte storage element after the charge / discharge cycle can be further improved.
  • the "main component” means the component having the highest content.
  • the second separator layer is further interposed between the positive electrode and the first separator layer. More specifically, at least one second separator layer is interposed between one surface of the negative electrode and the first separator layer, and the other at least one second separator layer is between the other surface of the positive electrode and the first separator layer. It is preferable to intervene in.
  • the second separator layer containing the inorganic particles By providing the second separator layer containing the inorganic particles on the side facing the positive electrode, the oxidation of the synthetic resin due to the direct contact of the first separator layer containing the synthetic resin as a main component with the positive electrode is suppressed.
  • the first separator layer can be protected.
  • the porosity of the second separator layer is 45% by volume or more and 85% by volume or less.
  • the porosity of the second separator layer is 45% by volume or more and 85% by volume or less, it is possible to suppress the occurrence of clogging of the pores of the second separator layer and to activate the negative electrode on the pores of the first separator layer. It is possible to suppress the invasion of the material layer.
  • the non-aqueous electrolyte power storage element includes a negative electrode, a positive electrode, and a non-aqueous electrolyte.
  • the non-aqueous electrolyte secondary battery will be described as an example of the non-aqueous electrolyte power storage element.
  • the positive electrode and the negative electrode form an electrode body that is alternately superimposed by laminating or winding via a first separator layer and a second separator layer.
  • the electrode body is housed in a case, and the case is filled with a non-aqueous electrolyte.
  • the non-aqueous electrolyte is interposed between the positive electrode and the negative electrode.
  • a known metal case, resin case or the like which is usually used as a case of a non-aqueous electrolyte secondary battery can be used.
  • the negative electrode has a negative electrode base material and a negative electrode active material layer.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material layer is laminated directly or via an intermediate layer along at least one surface of the negative electrode base material.
  • the negative electrode base material is a base material having conductivity.
  • a metal such as copper, nickel, stainless steel, nickel-plated steel or an alloy thereof is used, and copper or a copper alloy is preferable.
  • examples of the form of the negative electrode base material include foil, a vapor-deposited film, a mesh, a porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, a copper foil or a copper alloy foil is preferable as the negative electrode base material.
  • Examples of the copper foil include rolled copper foil and electrolytic copper foil. Whether or not having a "conductive" is the volume resistivity is measured according to JIS-H-0505 (1975 years) is equal to 1 ⁇ 10 7 ⁇ ⁇ cm as a threshold value.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material layer contains an acrylic resin as a binder.
  • the negative electrode active material can be appropriately selected from known negative electrode active materials.
  • a material capable of occluding and releasing lithium ions is usually used.
  • the negative electrode active material include metal Li; metal or semi-metal such as Si and Sn; metal oxide or semi-metal oxide such as Si oxide, Ti oxide and Sn oxide; Li 4 Ti 5 O 12 ; Titanium-containing oxides such as LiTIO 2 and TiNb 2 O 7 ; polyphosphate compounds; silicon carbide; non-graphites such as graphite (graphite), non-graphitizable carbon (hard carbon) and easily graphitizable carbon (soft carbon). Examples include carbon materials such as carbon. Among these materials, graphite and non-graphitic carbon are preferable. In the negative electrode active material layer, one of these materials may be used alone, or two or more of them may be mixed and used.
  • Graphite refers to a carbon material having an average lattice spacing (d 002 ) of (002) planes determined by X-ray diffraction before charging / discharging or in a discharged state of 0.33 nm or more and less than 0.34 nm. Examples of graphite include natural graphite and artificial graphite.
  • Non-graphitic carbon refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane determined by X-ray diffraction before charging / discharging or in a discharged state of 0.34 nm or more and 0.42 nm or less.
  • non-graphitizable carbon examples include non-graphitizable carbon and easily graphitizable carbon.
  • the non-planar carbon examples include a resin-derived material, a petroleum pitch or a petroleum pitch-derived material, a petroleum coke or a petroleum coke-derived material, a plant-derived material, an alcohol-derived material, and the like.
  • the “non-graphitizable carbon” refers to a carbon material having d 002 of 0.36 nm or more and 0.42 nm or less.
  • the “graphitizable carbon” refers to a carbon material having d 002 of 0.34 nm or more and less than 0.36 nm.
  • the discharged state means a state in which the carbon material, which is the negative electrode active material, is discharged so as to sufficiently release lithium ions that can be occluded and discharged by charging and discharging.
  • the open circuit voltage is 0.7 V or more.
  • the content of the negative electrode active material in the negative electrode active material layer is not particularly limited, but the lower limit thereof is preferably 50% by mass, more preferably 80% by mass, and even more preferably 90% by mass. On the other hand, the upper limit of this content is preferably 99% by mass, more preferably 98% by mass.
  • the negative electrode active material layer includes typical non-metal elements such as B, N, P, F, Cl, Br, I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba and the like.
  • Typical metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Ta, Hf, Nb, W, etc. It may be contained as a component other than the thickener and the filler.
  • the negative electrode active material is usually particles (powder).
  • the average particle size of the negative electrode active material can be, for example, 1 nm or more and 100 ⁇ m or less.
  • the negative electrode active material is a carbon material, a titanium-containing oxide or a polyphosphoric acid compound
  • the average particle size thereof may be 1 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode active material is Si, Sn, Si oxide, Sn oxide or the like
  • the average particle size thereof may be 1 nm or more and 1 ⁇ m or less.
  • the electron conductivity of the active material layer is improved.
  • a crusher, a classifier, or the like is used to obtain a powder having a predetermined particle size.
  • the negative electrode active material is a metal such as metal Li
  • the negative electrode active material may be in the form of a foil.
  • the negative electrode active material layer contains an acrylic resin as a binder.
  • acrylic resin examples include a polymer of an acrylic acid ester or a methacrylic acid ester, a copolymer containing polyacrylamide, an acrylic acid ester or a methacrylic acid ester, and the like.
  • the content of the acrylic resin in the binder is preferably 99% by mass or more, and may be 100% by mass.
  • the lower limit of the content of the binder in the negative electrode active material layer is preferably 0.2% by mass, more preferably 0.3% by mass, 0.4% by mass, or 0.5% by mass from the viewpoint of ensuring adhesion. In some cases, 0.8% by mass is even more preferable, 0.9% by mass is even more preferable, and 1.0% by mass is particularly preferable. On the other hand, as the upper limit of this content, from the viewpoint of improving output performance, 10% by mass is preferable, 5% by mass is more preferable, 3% by mass, 2% by mass% and 1% by mass are more preferable, and 0.8% by mass. May be particularly preferred.
  • the negative electrode active material layer contains optional components such as a conductive agent, a thickener, and a filler, if necessary.
  • the conductive agent is not particularly limited as long as it is a conductive material.
  • the carbon materials such as graphite, graphitizable carbon, and non-graphitizable carbon also have conductivity, but are not included in the conductive agent in the negative electrode active material layer.
  • Examples of the conductive agent other than the carbon material include other carbonaceous materials, metals, conductive ceramics and the like.
  • Examples of other carbonaceous materials include other non-graphitic carbons, graphene-based carbons and the like.
  • Examples of other non-graphular carbons include carbon nanofibers, pitch-based carbon fibers, and carbon black. Examples of carbon black include furnace black, acetylene black, and ketjen black.
  • Examples of graphene-based carbons include graphene, carbon nanotubes (CNTs), fullerenes and the like.
  • Examples of the shape of the conductive agent include powder and fibrous.
  • As the conductive agent one of these materials may be used alone, or two or more of them may be mixed and used. Further, these materials may be combined and used. For example, a material in which carbon black and CNT are combined may be used. Among these, carbon black is preferable from the viewpoint of electron conductivity and coatability, and acetylene black is particularly preferable.
  • the thickener examples include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose.
  • CMC carboxymethyl cellulose
  • methyl cellulose examples include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose.
  • the filler is not particularly limited.
  • the main component of the filler include polyolefins such as polypropylene and polyethylene, silica, alumina, zeolite, and glass.
  • the lower limit of the average thickness of one side of the negative electrode active material layer is not particularly limited, but may be 30 ⁇ m, preferably 40 ⁇ m, 44 ⁇ m, 49 ⁇ m, 50 ⁇ m, and 55 ⁇ m, 59 ⁇ m, 60 ⁇ m, or 62 ⁇ m. More preferably, 64 ⁇ m is even more preferable.
  • the average thickness of one side of the negative electrode active material layer is at least the above lower limit, the energy density of the non-aqueous electrolyte power storage element can be increased.
  • the upper limit of the average thickness of one side of the negative electrode active material layer is not particularly limited, but may be 90 ⁇ m, preferably 80 ⁇ m, 79 ⁇ m, or 77 ⁇ m, and more preferably 75 ⁇ m, 74 ⁇ m, or 72 ⁇ m. ..
  • the average thickness of one side of the negative electrode active material layer is not more than the above upper limit, the output performance of the non-aqueous electrolyte power storage element can be improved, and the negative electrode active material layer penetrates into the pores of the first separator layer. This can be suppressed, and clogging of the first separator layer can be suppressed with high certainty.
  • the average thickness of one side of the negative electrode active material layer is preferably 50 ⁇ m or more and 90 ⁇ m or less, and more preferably 62 ⁇ m or more and 77 ⁇ m or less.
  • the average thickness of one side of the negative electrode active material layer is preferably 30 ⁇ m or more and 50 ⁇ m or less, preferably 32 ⁇ m, from the viewpoint of improving output performance. More preferably 48 ⁇ m or more.
  • the intermediate layer is a coating layer on the surface of the negative electrode base material, and contains a conductive agent such as carbon particles to reduce the contact resistance between the negative electrode base material and the negative electrode active material layer.
  • the composition of the intermediate layer is not particularly limited, and can be formed by, for example, a composition containing a binder and a conductive agent.
  • the positive electrode has a positive electrode base material and a positive electrode active material layer.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material layer is laminated directly or via an intermediate layer along at least one surface of the positive electrode base material.
  • the configuration of the intermediate layer is not particularly limited, and can be selected from, for example, the configurations exemplified by the negative electrode.
  • the positive electrode base material is a base material having conductivity.
  • metals such as aluminum, titanium, tantalum, and stainless steel or alloys thereof are used.
  • aluminum and aluminum alloys are preferable from the viewpoint of the balance between potential resistance, high conductivity and cost.
  • Examples of the form of the positive electrode base material include foil, a vapor-deposited film, a mesh, a porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode base material.
  • aluminum or aluminum alloy include A1085, A3003, and A1N30 specified in JIS-H4000 (2014) or JIS-H4160 (2006).
  • the average thickness of the positive electrode substrate is preferably 3 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 40 ⁇ m or less, further preferably 8 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the positive electrode active material layer contains a positive electrode active material.
  • a positive electrode active material for example, a known positive electrode active material can be appropriately selected.
  • a material capable of occluding and releasing lithium ions is usually used.
  • the positive electrode active material include a lithium transition metal composite oxide having an ⁇ -NaFeO type 2 crystal structure, a lithium transition metal composite oxide having a spinel type crystal structure, a polyanionic compound, a chalcogen compound, sulfur and the like.
  • lithium transition metal composite oxide having an ⁇ -NaFeO type 2 crystal structure examples include Li [Li x Ni (1-x) ] O 2 (0 ⁇ x ⁇ 0.5) and Li [Li x Ni ⁇ Co (0 ⁇ x ⁇ 0.5).
  • Examples of the lithium transition metal composite oxide having a spinel-type crystal structure include Li x Mn 2 O 4 and Li x Ni ⁇ Mn (2- ⁇ ) O 4 .
  • Examples of the polyanionic compound include LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , Li 2 CoPO 4 F and the like.
  • Examples of the chalcogen compound include titanium disulfide, molybdenum disulfide, molybdenum dioxide and the like. The atoms or polyanions in these materials may be partially substituted with atoms or anion species consisting of other elements.
  • the lithium transition metal composite oxide is preferable as the positive electrode active material from the viewpoint of increasing energy density, and a nickel cobalt manganese-containing lithium transition metal composite containing nickel, cobalt and manganese as constituent elements in addition to Li is preferable. Oxides are more preferred.
  • the surface of the material listed as the positive electrode active material may be coated with another material.
  • one of these materials may be used alone, or two or more of them may be mixed and used.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but the lower limit thereof is preferably 50% by mass, more preferably 80% by mass, and even more preferably 90% by mass. On the other hand, as the upper limit of this content, 99% by mass is preferable, and 98% by mass is more preferable.
  • the positive electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, and a filler, if necessary.
  • Optional components such as a conductive agent, a binder, a thickener, and a filler can be selected from the materials exemplified for the negative electrode.
  • carbon materials such as graphite, graphitizable carbon, and non-graphitizable carbon are also included in the conductive agent.
  • the binder of the positive electrode active material layer is not particularly limited, and is, for example, a fluororesin (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), a thermoplastic resin such as polyethylene, polypropylene, polyimide; ethylene-propylene-.
  • Elastomers such as diene rubber (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), and fluororubber; polysaccharide polymers and the like can be mentioned.
  • the non-aqueous electrolyte power storage element includes a first separator layer and a second separator layer.
  • the first separator layer is interposed between the negative electrode and the positive electrode
  • the second separator layer is interposed between the negative electrode and the first separator layer.
  • the first separator layer and the second separator layer are infiltrated with a non-aqueous electrolyte.
  • the first separator layer and the second separator layer separate the positive electrode and the negative electrode, and hold a non-aqueous electrolyte between the positive electrode and the negative electrode.
  • the porosity of the second separator layer is higher than the porosity of the first separator layer.
  • the non-aqueous electrolyte power storage element has a charge / discharge cycle in which a second separator layer having a higher porosity than the first separator layer is arranged facing the negative electrode active material layer using an acrylic resin as a binder. The effect of suppressing the subsequent increase in resistance is improved.
  • the lower limit of the porosity of the first separator layer is preferably 30%, more preferably 31%, 32%, 33%, 34%, or 35%, and 36%, 37%, 38. %, 39%, or 40% may be preferred.
  • the porosity of the first separator layer By setting the porosity of the first separator layer to be equal to or higher than the above lower limit, the permeability of the non-aqueous electrolyte can be improved.
  • the upper limit of the porosity of the first separator layer is preferably 50%, more preferably 49%, 48%, 47%, 46%, or 45%, and 44%, 43%. , 42%, 41%, or 40% is more preferred. By setting the porosity of the first separator layer to the above upper limit or less, the strength of the first separator layer can be improved.
  • the lower limit of the porosity of the second separator layer is preferably 45%, more preferably 46%, 47%, 48%, 49% or 50%.
  • the porosity of the second separator layer By setting the porosity of the second separator layer to be equal to or higher than the above lower limit, the permeability of the non-aqueous electrolyte can be improved.
  • the upper limit of the porosity of the second separator layer may be 90%, preferably 88%, 87%, 86%, or 85%, and 84%, 83%, 82%, 81%, and so on. Or 80% is more preferable. By setting the porosity of the second separator layer to the above upper limit or less, the strength of the second separator layer can be improved.
  • the difference between the porosity of the first separator layer and the porosity of the second separator layer is preferably 5% or more and 55% or less, more preferably 8% or more and 49% or less, and further preferably 9% or more and 48% or less. It is preferable, and 10% or more and 45% or less are particularly preferable.
  • the porosity of the first separator layer and the second separator layer is calculated from the following formula.
  • W is the mass [g / cm 2 ] per unit area of the first separator layer and the second separator layer
  • ⁇ is the true density [g / cm 2] of the material constituting the first separator layer or the second separator layer. cm 3 ], where t is the thickness [cm] of the first separator layer or the second separator layer.
  • Porosity (%) 100- (W / ( ⁇ ⁇ t)) ⁇ 100
  • the first separator layer preferably contains a synthetic resin as a main component. Since the first separator layer contains a synthetic resin as a main component, the strength is excellent.
  • the synthetic resin as the main component of the first separator layer is not particularly limited, and examples thereof include polyolefins, polyesters, polyimides, polyamides (aromatic polyamides, aliphatic polyamides, etc.) and the like. Polyolefins shall also include copolymers of olefins and other monomers.
  • polystyrene resin examples include polyethylene (PE), polypropylene (PP), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene and the like.
  • polyolefin derivative examples include a polyolefin derivative and an ethylene-propylene copolymer.
  • polyolefins polyolefins, polyesters and aliphatic polyamides are preferable, polyolefins are more preferable, and PE and PP are even more preferable. PE and PP can exert a good shutdown function.
  • the structure of the first separator layer for example, a woven fabric, a non-woven fabric, a microporous film, or the like is used.
  • a non-woven fabric and a microporous membrane are preferable, and a microporous membrane is more preferable.
  • the microporous membrane has advantages such as high strength.
  • Nonwoven fabric has advantages such as high liquid retention.
  • the second separator layer preferably contains inorganic particles. Since the second separator layer contains inorganic particles, the effect of suppressing the invasion of the negative electrode active material layer into the pores of the first separator layer can be enhanced, so that the resistance of the non-aqueous electrolyte power storage element increases after the charge / discharge cycle. It is possible to further improve the suppressive effect on.
  • the second separator layer is a porous layer.
  • the second separator layer is usually composed of inorganic particles and a binder, and may contain other components.
  • Examples of the inorganic particles contained in the second separator layer include oxides such as alumina, silica, zirconia, titania, magnesia, ceria, ittria, zinc oxide and iron oxide, nitrides such as silicon nitride, titanium nitride and boron nitride, and silicon.
  • oxides such as alumina, silica, zirconia, titania, magnesia, ceria, ittria, zinc oxide and iron oxide
  • nitrides such as silicon nitride, titanium nitride and boron nitride, and silicon.
  • Carbide calcium silicate, aluminum sulfate, barium sulfate, aluminum hydroxide, potassium titanate, barium titanate, talc, kaolin ray, kaolinite, halloysite, pyrophyllite, montmorillonite, sericite, mica, amesite, bentonite, asbestos , Ox
  • binder for the second separator layer include those exemplified as the binder for the positive electrode active material layer described above.
  • the second separator layer may be integrally formed with the first separator layer, or may be in a form independent of the first separator layer. Further, the second separator layer may be provided so as to cover the negative electrode active material layer.
  • the second separator layer is further interposed between the positive electrode and the first separator layer. More specifically, at least one second separator layer is interposed between one surface of the negative electrode and the first separator layer, and the other at least one second separator layer is between the other surface of the positive electrode and the first separator layer. It is preferable to intervene in.
  • the synthetic resin is oxidized by the direct contact of the first separator layer containing the synthetic resin as a main component with the positive electrode. It can be suppressed and the first separator layer can be protected.
  • the lower limit of the average thickness of the first separator layer is preferably 4 ⁇ m, more preferably 8 ⁇ m.
  • the upper limit of this average thickness is preferably 30 ⁇ m, more preferably 20 ⁇ m.
  • the lower limit of the average thickness of the second separator layer is preferably 1 ⁇ m, more preferably 2 ⁇ m.
  • the upper limit of the average thickness of the second separator layer is preferably 10 ⁇ m, more preferably 6 ⁇ m.
  • the ratio of the average thickness of the second separator layer to the average thickness of the first separator layer is preferably less than 0.5, preferably 0.4 or less, and more preferably 0.3 or less.
  • the lower limit of the ratio of the average thickness of the second separator layer to the average thickness of the first separator layer is preferably 0.1 or more, more preferably 0.2 or more.
  • the ratio of the average thickness of the second separator layer to the average thickness of the first separator layer is equal to or higher than the above lower limit, it is possible to prevent the negative electrode active material layer from invading the pores of the first separator layer. It is possible to prevent the separator layer from being clogged with high certainty.
  • the lower limit of the ratio of the average thickness of the first separator layer to the average thickness of the negative electrode active material layer and the total thickness of the second separator layer is, for example, 0.05, and may be 0.10. , 0.15 is preferable, 0.20 is more preferable, and 0.25, 0.30, 0.38 may be preferable.
  • the upper limit of the ratio of the average thickness of the first separator layer to the average thickness of the negative electrode active material layer and the total thickness of the second separator layer is, for example, 1.30, preferably 1.00. , 0.80, 0.75, 0.65 are more preferable, and 0.60, 0.50, 0.45 may be preferable.
  • the energy density of the non-aqueous electrolyte power storage element can be adjusted.
  • the lower limit of the ratio of the average thickness of the first separator layer to the average thickness of the negative electrode active material layer is, for example, 0.04, preferably 0.08, and more preferably 0.11.
  • the upper limit of the ratio of the average thickness of the first separator layer to the average thickness of the negative electrode active material layer is, for example, 1.00, 0.80, 0.70, 0.65, 0.50, 0. It may be .45, and 0.40 or 0.30 may be preferable.
  • the lower limit of the ratio of the average thickness of the second separator layer to the average thickness of the negative electrode active material layer is, for example, 0.01, preferably 0.02, 0.04, 0.06, 0.08. Is more preferable.
  • the upper limit of the ratio of the average thickness of the second separator layer to the average thickness of the negative electrode active material layer is, for example, 0.33, preferably 0.20, 0.17, 0.13, and 0.10. , 0.08.
  • the upper limit charging potential of the positive electrode is 4.15 V vs. from the viewpoint of suppressing the oxidation of the first separator layer. .. Li / Li + or less is preferable, and 4.10 V vs. Li / Li + or less is more preferable.
  • the charge upper limit voltage of the non-aqueous electrolyte power storage element may be controlled by setting a charger or the like, but the charge / discharge reaction potential of LiFePO 4 or the like as the positive electrode active material. Is 4.15V vs. Materials that are Li / Li + or less may be used.
  • Non-water electrolyte As the non-aqueous electrolyte, a known non-aqueous electrolyte can be appropriately selected. As the non-aqueous electrolyte, a non-aqueous electrolyte solution is used. The non-aqueous electrolyte solution contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • Non-aqueous solvent a known non-aqueous solvent can be appropriately selected.
  • the non-aqueous solvent include cyclic carbonates, chain carbonates, carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, ethers, amides, nitriles and the like.
  • a solvent in which some of the hydrogen atoms contained in these compounds are replaced with halogen may be used.
  • cyclic carbonate examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinylethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), and difluoroethylene.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • VEC vinylene carbonate
  • VEC vinylethylene carbonate
  • FEC fluoroethylene carbonate
  • difluoroethylene examples thereof include carbonate (DFEC), styrene carbonate, catechol carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate, and among these, EC is preferable.
  • chain carbonate examples include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diphenyl carbonate, trifluoroethylmethyl carbonate, bis (trifluoroethyl) carbonate and the like.
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethylmethyl carbonate
  • diphenyl carbonate trifluoroethylmethyl carbonate
  • bis (trifluoroethyl) carbonate bis (trifluoroethyl) carbonate and the like.
  • EMC is preferable.
  • the non-aqueous solvent it is preferable to use cyclic carbonate or chain carbonate, and it is more preferable to use cyclic carbonate and chain carbonate in combination.
  • the cyclic carbonate By using the cyclic carbonate, the dissociation of the electrolyte salt can be promoted and the ionic conductivity of the non-aqueous electrolyte solution can be improved.
  • the chain carbonate By using the chain carbonate, the viscosity of the non-aqueous electrolytic solution can be kept low.
  • the volume ratio of the cyclic carbonate to the chain carbonate is preferably in the range of, for example, 5:95 to 50:50.
  • the electrolyte salt can be appropriately selected from known electrolyte salts.
  • Examples of the electrolyte salt include lithium salt, sodium salt, potassium salt, magnesium salt, onium salt and the like. Of these, lithium salts are preferred.
  • Lithium salts include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2). C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiC (SO 2 C 2 F 5 ) 3 and other halogenated hydrocarbon groups Examples thereof include lithium salts having. Among these, an inorganic lithium salt is preferable, and LiPF 6 is more preferable.
  • the content of the electrolyte salt in the nonaqueous electrolytic solution preferable to be 0.1 mol / dm 3 or more 2.5 mol / dm 3 or less, more preferable to be 0.3 mol / dm 3 or more 2.0 mol / dm 3 or less , more preferable to be 0.5 mol / dm 3 or more 1.7 mol / dm 3 or less, and particularly preferably 0.7 mol / dm 3 or more 1.5 mol / dm 3 or less.
  • the non-aqueous electrolyte solution may contain additives.
  • the additive include aromatic compounds such as biphenyl, alkyl biphenyl, terphenyl, and partially hydrides of turphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; 2-fluorobiphenyl, o.
  • -Partial halides of the above aromatic compounds such as cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; Halogenated anisole compounds; succinic anhydride, glutaric anhydride, maleic anhydride, citraconic anhydride, glutaconic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride; ethylene sulfone, propylene sulfite, dimethyl sulfite, dimethyl sulfate, ethylene sulfate, Sulfone, dimethyl sulfone, diethyl sulfone, dimethyl sulfoxide, diethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfide, 4,4'-bis (2,2-dioxo-1,3,2-dioxathiolane), 4-methylsulfonyloxymethyl- Examples thereof
  • the content of the additive contained in the non-aqueous electrolytic solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass or more and 7% by mass or less with respect to the total mass of the non-aqueous electrolytic solution. , 0.2% by mass or more and 5% by mass or less is more preferable, and 0.3% by mass or more and 3% by mass or less is particularly preferable.
  • non-aqueous electrolyte a non-aqueous electrolyte solution and a solid electrolyte may be used in combination.
  • the shape of the non-aqueous electrolyte power storage element of the present embodiment is not particularly limited, and examples thereof include a cylindrical battery, a pouch film type battery, a square battery, a flat type battery, a coin type battery, and a button type battery. Be done.
  • FIG. 1 shows a non-aqueous electrolyte power storage element 1 as an example of a square battery.
  • the figure is a perspective view of the inside of the case 3.
  • the electrode body 2 having the positive electrode and the negative electrode wound around the separator is housed in the square case 3.
  • the positive electrode is electrically connected to the positive electrode terminal 4 via the positive electrode current collector 41.
  • the negative electrode is electrically connected to the negative electrode terminal 5 via the negative electrode current collector 51. Further, a non-aqueous electrolyte is injected into the case 3.
  • the method for manufacturing a non-aqueous electrolyte power storage element includes accommodating the negative electrode, the positive electrode, and the non-aqueous electrolyte in a case.
  • the negative electrode can be obtained by laminating the negative electrode active material layer directly on the negative electrode base material or via an intermediate layer.
  • the laminating of the negative electrode active material layer is performed by applying a negative electrode mixture paste containing a negative electrode active material and an acrylic resin to the negative electrode base material.
  • the positive electrode can be obtained by laminating the positive electrode active material layer directly on the positive electrode base material or via an intermediate layer, similarly to the negative electrode.
  • the laminating of the positive electrode active material layer is performed by applying a positive electrode mixture paste to the positive electrode base material.
  • the negative electrode mixture paste and the positive electrode mixture paste may contain a dispersion solvent.
  • the dispersion solvent for example, an aqueous solvent such as water or a mixed solvent mainly composed of water; an organic solvent such as N-methylpyrrolidone or toluene can be used.
  • the method for manufacturing the non-aqueous electrolyte power storage element includes laminating the negative electrode and the positive electrode via the first separator layer and the second separator layer.
  • the first separator layer is interposed between the negative electrode and the positive electrode
  • the second separator layer is interposed between the negative electrode and the first separator layer.
  • An electrode body is formed by laminating the negative electrode and the positive electrode via the first separator layer and the second separator layer.
  • the method of accommodating the negative electrode, the positive electrode, the non-aqueous electrolyte, etc. in the case can be performed by a known method. After accommodating, a non-aqueous electrolyte power storage element can be obtained by sealing the accommodating port. The details of each element constituting the non-aqueous electrolyte power storage element obtained by the above manufacturing method are as described above.
  • the non-aqueous electrolyte power storage device of the present invention is not limited to the above embodiment, and various modifications may be made without departing from the gist of the present invention.
  • the configuration of one embodiment can be added to the configuration of another embodiment, and a part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a well-known technique.
  • some of the configurations of certain embodiments can be deleted.
  • a well-known technique can be added to the configuration of a certain embodiment.
  • the non-aqueous electrolyte storage element has been described mainly in the form of a non-aqueous electrolyte secondary battery, but other non-aqueous electrolyte storage elements may be used.
  • examples of other non-aqueous electrolyte storage elements include capacitors (electric double layer capacitors, lithium ion capacitors) and the like.
  • Examples of the non-aqueous electrolyte secondary battery include a lithium ion non-aqueous electrolyte secondary battery.
  • the winding type electrode body is used, but the laminated type formed from the laminated body in which a plurality of sheet bodies including the positive electrode, the negative electrode, the first separator layer and the second separator layer are stacked.
  • An electrode body may be provided.
  • the present invention can also be realized as a power storage device including a plurality of the above-mentioned non-aqueous electrolyte electric elements.
  • a power storage unit can be configured by using a single or a plurality of non-aqueous electrolyte power storage elements of the present invention, and a power storage device can be further configured by using the power storage unit.
  • the power storage device can be used as a power source for automobiles such as electric vehicles (EVs), hybrid electric vehicles (HEVs), and plug-in hybrid vehicles (PHEVs).
  • the power storage device can be used for various power supply devices such as an engine starting power supply device, an auxiliary power supply device, and an uninterruptible power supply (UPS).
  • UPS uninterruptible power supply
  • FIG. 2 shows an example of a power storage device 30 in which a power storage unit 20 in which two or more electrically connected non-aqueous electrolyte power storage elements 1 are assembled is further assembled. Even if the power storage device 30 includes a bus bar (not shown) for electrically connecting two or more non-aqueous electrolyte power storage elements 1 and a bus bar (not shown) for electrically connecting two or more power storage units 20. good.
  • the power storage unit 20 or the power storage device 30 may include a condition monitoring device (not shown) for monitoring the state of one or more non-aqueous electrolyte power storage elements.
  • Example 1 and Comparative Example 2 (Negative electrode) A negative electrode mixture paste containing graphite as a negative electrode active material, the binder shown in Table 1, and carboxymethyl cellulose (CMC) as a thickener, and using water as a dispersion solvent was prepared. The mixing ratio of the negative electrode active material, the binder and the thickener was 98: 1: 1 in mass ratio. The negative electrode mixture paste is applied to one side of a copper foil having a thickness of 10 ⁇ m as a negative electrode base material, dried and pressed to form a negative electrode active material layer having an average thickness of 67 ⁇ m, and the negative electrodes of Examples and Comparative Examples are formed.
  • CMC carboxymethyl cellulose
  • a positive electrode mixture paste containing the above positive electrode active material, polyvinylidene fluoride (PVDF) as a binder, and acetylene black as a conductive agent and using N-methyl-2-pyrrolidone (NMP) as a dispersion solvent was prepared. ..
  • the mixing ratio of the positive electrode active material, the binder and the conductive agent was 94: 3: 3 in mass ratio.
  • the positive electrode mixture paste was applied to one side of the positive electrode base material, dried and pressed to form a positive electrode active material layer.
  • An aluminum foil having a thickness of 15 ⁇ m was used as the positive electrode base material.
  • the separator has a porous layer containing inorganic particles and a binder (average thickness 4 ⁇ m, porosity 48%) on one side of a microporous substrate made of polyolefin (average thickness 20 ⁇ m, porosity 37%).
  • a microporous substrate made of polyolefin average thickness 20 ⁇ m, porosity 37%).
  • the microporous substrate made of polyolefin corresponds to the first separator layer
  • the porous layer corresponds to the second separator layer.
  • a non-aqueous electrolyte power storage element using the positive electrode and the negative electrode was assembled.
  • the positive electrode active material layer and the negative electrode active material layer face each other with the first separator layer and the second separator layer interposed therebetween, the first separator layer is interposed between the negative electrode and the positive electrode, and the second separator layer is the negative electrode.
  • the positive electrode, the first separator layer, the second separator layer and the negative electrode were laminated so as to be interposed between the first separator layers, and the non-aqueous electrolyte was used as the non-aqueous electrolyte.
  • Example 2 and Comparative Example 3 As a separator, a porous layer containing inorganic particles and a binder on both sides of a microporous base material made of polyolefin (average thickness 14 ⁇ m, porosity 45%) (average thickness 3 ⁇ m, porosity: 58%). We used the laminated ones.
  • the microporous base material made of polyolefin corresponds to the first separator layer
  • the porous layer corresponds to the second separator layer.
  • the positive electrode, the first separator layer, the second separator layer and the negative electrode are laminated so that one second separator layer is interposed between the negative electrode and the first separator layer and the other second separator layer is interposed between the positive electrode and the first separator layer.
  • the non-aqueous electrolyte power storage elements of Example 2 and Comparative Example 3 were obtained in the same manner as in Example 1 and Comparative Example 2 except for the above.
  • Comparative Example 1 and Comparative Example 4 As a separator, a porous layer containing inorganic particles and a binder (average thickness 4 ⁇ m, porosity: 75%) on one side of a microporous base material made of polyolefin (average thickness 14 ⁇ m, porosity 44%). was used.
  • the microporous base material made of polyolefin corresponds to the first separator layer
  • the porous layer corresponds to the second separator layer.
  • the positive electrode, the first separator layer, the second separator layer and the negative electrode are laminated so that the second separator layer is interposed between the positive electrode active material and the first separator layer. Then, the non-aqueous electrolyte power storage elements of Comparative Example 1 and Comparative Example 4 were obtained.
  • each of the obtained non-aqueous electrolyte power storage elements was subjected to constant current charging at 25 ° C. with a charging current of 1.0 C to set the SOC (State of Charge) to 50%. It was charged at 25 ° C. with a charging current of 0.2C, 0.5C, or 1.0C for 30 seconds. After each charge was completed, constant current discharge was performed with a discharge current of 1.0 C to set the SOC to 50%. The relationship between the current at each charging current and the voltage 10 seconds after the start of charging was plotted, and the DC input resistance (initial DC input resistance) was obtained from the slope of a straight line obtained from the three plots.
  • the negative electrode active material layer contains an acrylic resin as a binder, and the second separator layer having a higher porosity than the first separator layer is not arranged facing the negative electrode.
  • Comparative Examples 2 to 3 in which the negative electrode active material layer contains styrene-butadiene rubber as a binder, the second separator layer is arranged facing the negative electrode even if the second separator is arranged facing the negative electrode. It can be seen that the DC input resistance increase rate after the charge / discharge cycle is not sufficiently reduced as compared with Comparative Example 4 which has not been used.
  • the non-aqueous electrolyte power storage element is excellent in the effect of suppressing the increase in resistance after the charge / discharge cycle.
  • the present invention is suitably used as a non-aqueous electrolyte power storage element such as a non-aqueous electrolyte secondary battery used as a power source for personal computers, electronic devices such as communication terminals, automobiles, and the like.
  • Non-aqueous electrolyte power storage element 1
  • Electrode body 3 Case 4
  • Positive electrode terminal 5
  • Negative electrode terminal 20
  • Power storage unit 30
  • Power storage device 41
  • Positive electrode current collector 51 Negative electrode current collector

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Abstract

Un élément de stockage d'énergie à électrolyte non aqueux selon un aspect de la présente invention comprend une électrode négative ayant une couche de matériau actif d'électrode négative contenant une résine acrylique, une électrode positive, une première couche de séparateur et une seconde couche de séparateur. La première couche de séparateur est interposée entre l'électrode négative et l'électrode positive. La seconde couche de séparateur est interposée entre l'électrode négative et la première couche de séparateur. La porosité de la seconde couche de séparateur est supérieure à celle de la première couche de séparateur.
PCT/JP2021/024557 2020-07-06 2021-06-29 Élément de stockage d'énergie à électrolyte non aqueux WO2022009734A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005011043A1 (fr) * 2003-07-29 2005-02-03 Matsushita Electric Industrial Co., Ltd. Accumulateur secondaire aux ions de lithium
JP2007018861A (ja) * 2005-07-07 2007-01-25 Nissan Motor Co Ltd 電池用セパレータおよびこれを用いた電池
WO2012014255A1 (fr) * 2010-07-29 2012-02-02 三菱重工業株式会社 Batterie secondaire aux ions de lithium
WO2016194589A1 (fr) * 2015-05-29 2016-12-08 日立マクセル株式会社 Batterie secondaire au lithium-ion
JP2017111894A (ja) * 2015-12-15 2017-06-22 株式会社豊田自動織機 リチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005011043A1 (fr) * 2003-07-29 2005-02-03 Matsushita Electric Industrial Co., Ltd. Accumulateur secondaire aux ions de lithium
JP2007018861A (ja) * 2005-07-07 2007-01-25 Nissan Motor Co Ltd 電池用セパレータおよびこれを用いた電池
WO2012014255A1 (fr) * 2010-07-29 2012-02-02 三菱重工業株式会社 Batterie secondaire aux ions de lithium
WO2016194589A1 (fr) * 2015-05-29 2016-12-08 日立マクセル株式会社 Batterie secondaire au lithium-ion
JP2017111894A (ja) * 2015-12-15 2017-06-22 株式会社豊田自動織機 リチウムイオン二次電池

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