WO2015053199A1 - Couche de substance active d'électrode pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant cette couche - Google Patents

Couche de substance active d'électrode pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant cette couche Download PDF

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Publication number
WO2015053199A1
WO2015053199A1 PCT/JP2014/076595 JP2014076595W WO2015053199A1 WO 2015053199 A1 WO2015053199 A1 WO 2015053199A1 JP 2014076595 W JP2014076595 W JP 2014076595W WO 2015053199 A1 WO2015053199 A1 WO 2015053199A1
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Prior art keywords
active material
electrode active
secondary battery
layer
material layer
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PCT/JP2014/076595
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English (en)
Japanese (ja)
Inventor
佐藤　一
堀江　英明
赤間　弘
雄太 村上
健一 川北
水野　雄介
都藤　靖泰
康裕 進藤
Original Assignee
日産自動車株式会社
三洋化成工業株式会社
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Publication of WO2015053199A1 publication Critical patent/WO2015053199A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 an electrode active material layer for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery using the same. More specifically, the present invention relates to a technique for suppressing a decrease in battery performance caused by expansion / contraction of an active material during charge / discharge.
  • hybrid vehicles HEV
  • electric vehicles EV
  • fuel cell vehicles have been manufactured and sold from the viewpoints of environment and fuel efficiency, and new developments are continuing.
  • a power supply device such as a lithium ion battery or a nickel metal hydride battery, an electric double layer capacitor, or the like is used.
  • lithium ion secondary batteries are considered suitable for electric vehicles because of their high energy density and high durability against repeated charging and discharging, and various developments have been intensively advanced.
  • connection portion causes a reduction in the output density and energy density of the battery.
  • a bipolar secondary battery is a power generator in which a positive electrode active material layer is formed on one surface of a current collector and a plurality of bipolar electrodes having a negative electrode active material layer formed on the other surface are stacked via an electrolyte layer. Has elements. In other words, the positive electrode active material layer, the electrolyte layer, and the negative electrode active material layer form one single cell layer, and a plurality of the single cell layers are stacked with the current collector interposed therebetween.
  • the active material contained in the positive electrode active material layer and the negative electrode active material layer has a characteristic that the volume expands and contracts by inserting and extracting lithium ions in the electrolyte during charge and discharge.
  • This expansion / shrinkage is a main cause of deterioration of cycle characteristics due to deformation of the battery structure or peeling of the active material layer from the current collector.
  • an active material having a large capacity has a large amount of lithium ions that are occluded and released, and therefore, expansion and contraction are more remarkable. That is, the battery capacity and the cycle characteristics are in a trade-off relationship, and various attempts have been made to improve the cycle characteristics even when an active material having a large capacity is used.
  • the insulation which consists of synthetic resin, rubber
  • a nonaqueous electrolyte secondary battery in which a protective layer is disposed has been proposed.
  • the insulating protective layer is characterized by having both an adhesive portion bonded to the outer peripheral surface of the electrode group and a non-adhered portion not bonded.
  • the electrode group is protected by adhering an insulating protective layer to the outer peripheral surface of the electrode group, and the insulating protective layer is provided along the outer peripheral surface without adhering partly (that is, the outer peripheral surface and the insulating protective layer are
  • the expansion stress in the direction perpendicular to the negative electrode current collector is relieved by providing a gap therebetween. This prevents deformation of the electrode group and dropping of the negative electrode active material from the current collector, and maintains cycle characteristics and safety over a long period of time.
  • an object of the present invention is to provide means capable of alleviating stress due to expansion / contraction of the active material in the electrode active material layer and improving the cycle characteristics of the battery.
  • the present inventors have conducted intensive research to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by constituting an electrode active material layer using a fibrous resin skeleton base material together with an active material, and the present invention has been completed.
  • the present invention includes a fibrous resin skeleton base material and an active material, wherein the active material is dispersed in voids of the fibrous resin skeleton base material. It is a material layer.
  • FIG. 1 is a cross-sectional view schematically showing a bipolar lithium ion secondary battery according to an embodiment of the present invention. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of a secondary battery.
  • An electrode active material layer for a non-aqueous electrolyte secondary battery includes a fibrous resin skeleton base material and an active material, and the active material is dispersed in voids of the fibrous resin skeleton base material. It is characterized by.
  • the structure of the electrode active material layer can be maintained even when the active material expands and contracts by including the fibrous resin skeleton base material.
  • the active material since the active material is dispersed in the voids of the fibrous resin skeleton base material (that is, there are voids in the vicinity of the active material), stress due to expansion and contraction of the active material is alleviated in all directions. Can be done. Therefore, by applying the electrode active material layer of the present invention to a non-aqueous electrolyte secondary battery, it becomes possible to improve the cycle characteristics of the non-aqueous electrolyte secondary battery.
  • the electrode active material layer for a non-aqueous electrolyte secondary battery is also simply referred to as “electrode active material layer” or “active material layer”.
  • electrode active material layer or “active material layer”.
  • bipolar lithium ion secondary batteries are simply “bipolar secondary batteries”
  • electrodes for bipolar lithium ion secondary batteries are simply “bipolar electrodes”
  • fibrous resin skeleton base materials are simply “base materials”. Also called.
  • FIG. 1 is a cross-sectional view schematically showing a part of an electrode active material layer according to an embodiment of the present invention.
  • the electrode active material layer 1 shown in FIG. 1 includes a fibrous resin skeleton base material 3 and a negative electrode active material 5, and the negative electrode active material 5 is a void (fibrous resin skeleton base material) of the fibrous resin skeleton base material 3.
  • 3 has a structure in which it is dispersed in a portion where 3 does not exist.
  • the fibrous resin skeleton base material 3 is composed of a conductive resin material in which acetylene black (not shown) as a conductive filler is dispersed in polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the negative electrode active material 5 is made of graphite.
  • acetylene black (not shown) is dispersed in the voids of the fibrous resin skeleton base material 3 as a conductive aid.
  • the fibrous resin skeleton base material 3 has a function of mainly maintaining the structure of the electrode active material layer.
  • skeleton base material 3 is comprised from the resin material which has electroconductivity as mentioned above. Therefore, the fibrous resin skeleton base material 3 can function as a conductive path from the negative electrode active material 5 to the current collector together with the conductive assistant.
  • the negative electrode active material 5 is dispersed in the voids of the fibrous resin skeleton base material 3, and the voids of the fibrous resin skeleton base material 3 can exist in the vicinity of the negative electrode active material 5. By the presence of the voids, the stress generated by the expansion / contraction of the negative electrode active material 5 during charge / discharge can be relaxed in all directions.
  • the components of the electrode active material layer 1 of this embodiment will be described.
  • the “fibrous resin skeleton base material” is a collection of resins formed into a fibrous shape (hereinafter also referred to as resin fibers), and has a function of mainly maintaining the structure of the electrode active material layer.
  • the aggregate form of the resin fibers is not particularly limited, and may be, for example, a non-woven fabric, a woven fabric, or a knitted fabric.
  • the resin constituting the fibrous resin skeleton base material is not particularly limited.
  • polyolefin such as polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE)), polypropylene (PP), polyethylene terephthalate (PET) ), Polyesters such as polybutylene terephthalate (PBT), polyether nitrile (PEN), polyacrylonitrile (PAN), polyurethane, polyimide (PI), polyamide, cellulose, carboxymethyl cellulose (CMC) and salts thereof, ethylene-vinyl acetate Polymer, polyvinyl chloride, styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene Lock copolymers and their hydrogenated products, thermoplastic polymers such as styrene /
  • polyethylene PE; high density polyethylene (HDPE), low density polyethylene (LDPE)), polyolefin such as polypropylene (PP), polyethylene terephthalate (PET), polyester such as polybutylene terephthalate (PBT), polyacrylonitrile (PAN).
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PET polyester
  • PBT polybutylene terephthalate
  • PAN polyacrylonitrile
  • PAN polyacrylonitrile
  • the fibrous resin skeleton base material can also function as a conductive path between the active material and the current collector by imparting conductivity. Therefore, it is preferable that the fibrous resin skeleton base material of this embodiment has conductivity.
  • a specific form in the case where the fibrous resin skeleton base material has conductivity is not particularly limited, but (1) a form in which the resin itself constituting the fibrous resin skeleton base material has conductivity; (2) fibrous form The form etc. which coat
  • Examples of the form (1a) include a form in which the resin constituting the fibrous resin skeleton base material is a conductive polymer.
  • a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, polyoxadiazole is used as a fibrous resin skeleton base material. Used as a constituent resin.
  • Fine particles made of a conductive material in the non-conductive polymer or conductive polymer exemplified above as the resin constituting the fibrous resin skeleton base material (Also referred to as a) is used.
  • the conductive material include carbon materials such as acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, fullerene, Al, Ti, Ni, Cu, Fe, etc. Examples thereof include metals and alloys containing the metals.
  • these electrically conductive materials may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the surface of the non-conductive polymer or the conductive polymer formed into a fibrous shape is the above-described surface.
  • examples include a form coated with a conductive material.
  • the amount of the conductive material used in the form (1b) or (2) is not particularly limited, but is preferably 5 to 35% by mass with respect to the resin constituting the fibrous resin skeleton base material. More preferably, it is 5 to 25% by mass, and further preferably 5 to 20% by mass.
  • the fibrous resin skeleton base material is a collection of the resin (resin fibers) formed into a fiber shape as described above, and has a certain gap between adjacent resin fibers as shown in FIG.
  • Such a fibrous resin skeleton base material preferably has the following shape characteristics from the viewpoints of maintaining the structure of the electrode active material layer, dispersing the active material, and penetrating the electrolytic solution (transfer of lithium ions).
  • the resin fibers constituting the fibrous resin skeleton base material preferably have a diameter of 0.1 to 100 ⁇ m, more preferably 0.1 to 10 ⁇ m, and an aspect ratio (long side / short side) of 1 to It is preferably 10,000 and more preferably 1 to 3000. If the diameter is 0.1 ⁇ m or more, it depends on the elastic modulus of the resin, but sufficient strength as a skeleton material can be obtained. If the diameter is 100 ⁇ m or less, the volume occupied by the skeleton material is the energy density of the battery. Can be reduced.
  • the pore diameter of the fibrous resin skeleton base material is preferably 10 to 300 ⁇ m, and more preferably 30 to 100 ⁇ m. If the pore diameter is 10 ⁇ m or more, the active material can be efficiently held in the pores, and if it is 300 ⁇ m or less, the electronic network formed by the active material and the fibrous resin skeleton functions sufficiently as a battery. It is possible to be within the range of the resistance value to be.
  • the porosity of the fibrous resin skeleton base material is preferably 70 to 98%, more preferably 80 to 98%.
  • the porosity is 70% or more, the active material can be retained without impairing the volumetric energy density of the battery, and when it is 98% or less, the function of retaining the active material can be expressed. is there.
  • the air permeability of the fibrous resin skeleton base material is preferably 0.5 to 50 cm 3 / cm 2 ⁇ sec, and more preferably 20 to 50 cm 3 / cm 2 ⁇ sec.
  • the porosity is 0.5 cm 3 / cm 2 ⁇ sec or more, the electrolyte solution can be sufficiently penetrated.
  • the porosity is 50 cm 3 / cm 2 ⁇ sec or less, the structure of the skeleton material can be maintained. is there.
  • the active material occludes and releases ions during charge and discharge to generate electrical energy.
  • the active material includes a positive electrode active material having a composition that occludes ions during discharging and releases ions during charging, and a negative electrode active material having a composition that can release ions during discharging and occlude ions during charging.
  • the electrode active material layer of this embodiment functions as a positive electrode active material layer when a positive electrode active material is used as the active material, and conversely functions as a negative electrode active material layer when a negative electrode active material is used. In this specification, the matters common to the positive electrode active material and the negative electrode active material are simply described as “active materials”.
  • the positive electrode active material examples include LiMn 2 O 4 , LiCoO 2 , LiNiO 2 , Li (Ni—Mn—Co) O 2, and lithium-- such as those in which some of these transition metals are substituted with other elements.
  • Examples include transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.
  • two or more positive electrode active materials may be used in combination.
  • a lithium-transition metal composite oxide is used as the positive electrode active material.
  • a composite oxide containing lithium and nickel is used, and more preferably Li (Ni—Mn—Co) O 2 and a part of these transition metals substituted with other elements (hereinafter, referred to as “following”) Simply referred to as “NMC composite oxide”).
  • the NMC composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in order) are stacked alternately via an oxygen atomic layer.
  • One Li atom is contained, and the amount of Li that can be taken out is twice that of the spinel lithium manganese oxide, that is, the supply capacity is doubled, so that a high capacity can be obtained.
  • the NMC composite oxide includes a composite oxide in which a part of the transition metal element is substituted with another metal element.
  • Other elements in that case include Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu , Ag, Zn, etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, From the viewpoint of improving cycle characteristics, Ti, Zr, Al, Mg, and Cr are more preferable.
  • a represents the atomic ratio of Li
  • b represents the atomic ratio of Ni
  • c represents the atomic ratio of Mn
  • d represents the atomic ratio of Co
  • x represents the atomic ratio of M. Represents. From the viewpoint of cycle characteristics, it is preferable that 0.4 ⁇ b ⁇ 0.6 in the general formula (1).
  • the composition of each element can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • Ti or the like partially replaces the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ x ⁇ 0.3 in the general formula (1). Since at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr is dissolved, the crystal structure is stabilized. It is considered that the battery capacity can be prevented from decreasing even if the above is repeated, and that excellent cycle characteristics can be realized.
  • b, c and d are 0.49 ⁇ b ⁇ 0.51, 0.29 ⁇ c ⁇ 0.31, 0.19 ⁇ d ⁇ 0.21. It is preferable from the viewpoint of improving the balance between capacity and life characteristics.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 is LiCoO 2 , LiMn 2 O 4 , LiNi 1/3 Mn 1/3 Co 1/3 O 2, etc. that have been proven in general consumer batteries.
  • the capacity per unit weight is large, and the energy density can be improved, so that a battery having a compact and high capacity can be produced, which is preferable from the viewpoint of cruising distance.
  • LiNi 0.8 Co 0.1 Al 0.1 O 2 is more advantageous in terms of a larger capacity, but there are difficulties in life characteristics.
  • LiNi 0.5 Mn 0.3 Co 0.2 O 2 has life characteristics as excellent as LiNi 1/3 Mn 1/3 Co 1/3 O 2 .
  • preferable negative electrode active materials include metals such as Si and Sn, or metal oxides such as TiO, Ti 2 O 3 , TiO 2 , SiO 2 , SiO, SnO 2 , and Li 4/3 Ti 5/3 O. 4 or Li 7 MnN and other complex oxides of lithium and transition metals, Li—Pb alloys, Li—Al alloys, Li, or graphite (natural graphite, artificial graphite), carbon black, activated carbon, carbon fiber, coke , Carbon materials such as soft carbon and hard carbon. Moreover, it is preferable that a negative electrode active material contains the element alloyed with lithium.
  • the above positive electrode active material or negative electrode active material may be used alone or in combination of two or more.
  • non-carbon active material When an active material other than the carbon material (hereinafter also referred to as “non-carbon active material”) is used, a material obtained by coating the surface of the non-carbon active material with a carbon material may be used as the active material. preferable. According to such a configuration, a conductive network is established between the active materials or between the active material and the conductive auxiliary agent described later, and even when an active material having a large expansion / contraction is used, the conductivity in the electrode A pass can be secured. As a result, it is possible to suppress an increase in resistance even when charging and discharging are repeated. More preferably, from the viewpoint of improving the energy density of the electrode, a material that is alloyed with high-capacity lithium is coated with a carbon material as the active material.
  • the coating amount of the carbon material is such that the electrical contact between the active materials or between the active material and the conductive additive is good depending on the particle size of the non-carbon active material (particle). do it.
  • the content is about 2 to 20% by mass with respect to the total mass of the coated active material.
  • the term “coating” includes not only the form in which the entire surface of the active material is covered with the carbon material but also the form in which the carbon material is present (attached) on a part of the surface of the active material. Shall be.
  • the average particle diameter of the active material is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m, from the viewpoint of battery capacity increase, reactivity, and cycle durability. Within such a range, the secondary battery can suppress an increase in the internal resistance of the battery during charging and discharging under high output conditions, and can extract a sufficient current.
  • the active material is secondary particles
  • the average particle diameter of the primary particles constituting the secondary particles is preferably in the range of 10 nm to 1 ⁇ m. It is not limited. However, it goes without saying that, depending on the production method, the active material may not be a secondary particle formed by aggregation, lump or the like.
  • the particle diameter of the active material and the particle diameter of the primary particles the median diameter obtained using a laser diffraction method can be used.
  • the shape of the active material varies depending on the type and manufacturing method, and examples thereof include a spherical shape (powder shape), a plate shape, a needle shape, a column shape, and a square shape, but are not limited thereto. Rather, any shape can be used without problems.
  • an optimal shape that can improve battery characteristics such as charge / discharge characteristics is appropriately selected.
  • a polymer that forms a gel by swelling of the liquid electrolyte on the surface of the core portion made of the active material and a conductive material. It is preferable to dispose a shell portion made of a functional material.
  • a gel-forming polymer a material having a certain degree of flexibility that can follow the expansion and contraction of an active material accompanying charging / discharging of a battery and is not easily broken (specifically, a tensile elongation at break in a gel state is 10% Use the above materials).
  • the constituent material of the gel-forming polymer may be a gel-forming polymer having a tensile elongation at break of 10% or more in the gel state as described above.
  • “Tensile elongation at break” is an index indicating the flexibility of the gel-forming polymer. Specifically, a value obtained by preparing a resin film, punching it into a dumbbell shape, immersing it in an electrolytic solution for a predetermined time, and measuring the tensile elongation at break in accordance with ASTM D683 (test piece shape Type II) It is.
  • the value of the tensile elongation at break of the gel-forming polymer may be 10% or more, preferably 20% or more, more preferably 30% or more, particularly preferably 40% or more, and most preferably Is 50% or more.
  • the value of the tensile elongation at break of the gel-forming polymer is preferably as large as possible from the viewpoint of solving the problems of the present invention.
  • a flexible partial structure eg, alkyl group, polyether residue, alkyl polycarbonate residue, alkyl
  • a method of introducing a polyester residue or the like into the main chain of the gel-forming polymer it is possible to adjust the tensile elongation at break by imparting flexibility to the gel-forming polymer by controlling the molecular weight of the gel-forming polymer or controlling the molecular weight between crosslinks.
  • the gel-forming polymer is preferably a polyurethane resin.
  • a polyurethane resin is used as the gel-forming polymer, first, there is an advantage that a shell portion having high flexibility (high tensile elongation at break) is formed. In addition, since urethane bonds can form strong hydrogen bonds, it is possible to form a gel-forming polymer that is structurally stable while being excellent in flexibility.
  • the specific form thereof is not particularly limited, and conventionally known knowledge about the polyurethane resin can be appropriately referred to.
  • the polyurethane resin is composed of (1) a polyisocyanate component and (2) a polyol component, and (3) an ionic group-introducing component, (4) an ionic group neutralizing agent component, and (5) chain extension as necessary. You may comprise using an agent component further.
  • polyisocyanate component examples include a diisocyanate compound having two isocyanate groups in one molecule and a polyisocyanate compound having three or more isocyanate groups in one molecule, and these are used alone. Alternatively, two or more kinds may be used in combination.
  • Diisocyanate compounds include 4,4'-diphenylmethane diisocyanate (MDI), 2,4- and / or 2,6-tolylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 3,3 Aromatic diisocyanates such as' -dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate; isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, norbornene Cycloaliphatic diisocyanates such as diisocyanates; 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trime Le hexamethylene diisocyanate, alipha
  • diisocyanate compounds may be used in the form of modified products such as carbodiimide modification, isocyanurate modification, biuret modification, etc., or may be used in the form of blocked isocyanates blocked with various blocking agents.
  • polyisocyanate compounds having three or more isocyanate groups in one molecule include, for example, isocyanurate trimers, biuret trimers, trimethylolpropane adducts of diisocyanates exemplified above; triphenylmethane triisocyanate, 1- Examples thereof include trifunctional or higher functional isocyanates such as methylbenzole-2,4,6-triisocyanate and dimethyltriphenylmethanetetraisocyanate.
  • isocyanate compounds are in the form of modified products such as carbodiimide modification, isocyanurate modification, biuret modification and the like. It may be used in the form of a blocked isocyanate blocked with various blocking agents.
  • Examples of the polyol component include a diol compound having two hydroxyl groups in one molecule and a polyol compound having three or more hydroxyl groups in one molecule, and these may be used alone. Two or more kinds may be used in combination.
  • diol compound and the polyol compound having three or more hydroxyl groups in one molecule examples include low molecular weight polyols, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or non-crystalline polycarbonate polyols, and polybutadiene.
  • a polyol and a silicone polyol are mentioned.
  • low molecular polyols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2-butyl-2-ethyl-1,3-propane.
  • polyether polyols examples include ethylene oxide adducts such as diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol; propylene oxide adducts such as dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and polypropylene glycol; These include low molecular weight polyol ethylene oxide and / or propylene oxide adducts, polytetramethylene glycol and the like.
  • polyester polyols include polyols such as the low molecular weight polyols exemplified above, and ester-forming derivatives such as polycarboxylic acids or their esters, anhydrides, halides, and the like in an amount less than the stoichiometric amount, and / or Examples thereof include those obtained by a direct esterification reaction and / or a transesterification reaction with a lactone or a hydroxycarboxylic acid obtained by hydrolytic ring-opening thereof.
  • polycarboxylic acids or ester-forming derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; trimellitic acid, trimesic acid, castor oil
  • Examples include lower aliphatic esters such as esters, butyl esters, isobutyl esters, and amyl esters.
  • Examples of the lactones include lactones such as ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, dimethyl- ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, and ⁇ -butyrolactone.
  • the ionic group-introducing component used as necessary includes an anionic group-introducing component and a cationic group-introducing component.
  • the anionic group to be introduced include polyols containing a carboxyl group such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, 1,4-butanediol-2-sulfonic acid, etc.
  • Polyols containing a sulfonic acid group of, for example, those for introducing a cationic group include N, N-dialkylalkanolamines, N-methyl-N, N-diethanolamine, N-butyl-N, N-alkyl-N, N-dialkanolamines such as N-diethanolamine and trialkanolamines can be mentioned.
  • the ionic group neutralizing agent component used as required includes anionic group neutralizing agents such as trialkylamines such as trimethylamine, triethylamine and tributylamine, N, N-dimethylethanolamine, N N, N-dimethylpropanolamine, N, N-dipropylethanolamine, N, N-dialkylalkanolamines such as 1-dimethylamino-2-methyl-2-propanol, N-alkyl-N, N-dialkanolamine , Tertiary amine compounds such as trialkanolamines such as triethanolamine; basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc., neutralizing cationic groups Agents include formic acid, acetic acid, lactic acid, succinic acid, gluta Organic carboxylic acids such as acid and citric acid, organic sulfonic acids such as paratoluenesulfonic acid and alkyl
  • chain extender component used as necessary, one or more known general chain extenders can be used, and polyvalent amine compounds, polyvalent primary alcohol compounds and the like are preferable, A polyvalent amine compound is more preferred.
  • the polyvalent amine compound include low molecular diamines in which the alcoholic hydroxyl groups of the above-illustrated low molecular diols such as ethylenediamine and propylenediamine are substituted with amino groups; polyethers such as polyoxypropylenediamine and polyoxyethylenediamine Diamines; mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis (3-aminopropyl) 2, Cycloaliphatic diamines such as 4,8,10-tetraoxaspiro (5,5) undecane; m-xyl
  • a diisocyanate compound is preferably used as the polyisocyanate component, and 4,4′-diphenylmethane diisocyanate (MDI), 2,4′-diphenylmethane diisocyanate, 4,4′-diisine. It is particularly preferable to use cyclohexanemethane diisocyanate, 1,4-cyclohexane diisocyanate, toluene-2,4-diisocyanate, 1,6-hexamethylene diisocyanate, and most preferably 4,4′-diphenylmethane diisocyanate (MDI). .
  • the (2) polyol component it is preferable to use an ethylene oxide adduct that is a diol compound, and it is particularly preferable to use polyethylene glycol. Since polyethylene glycol is excellent in lithium ion conductivity, the effect of reducing (raising suppression) the internal resistance of the battery can be remarkably exhibited by adopting such a configuration.
  • the number average molecular weight calculated from the hydroxyl value of polyethylene glycol is not particularly limited, but is preferably 2,500 to 15,000, more preferably 3,000 to 13,000, and still more preferably 3 , 500 to 10,000. From the viewpoint of heat resistance, it is preferable to further use ethylene glycol and / or glycerin as the polyol component in addition to the essential components described above.
  • the gel obtained by swelling the gel-forming polymer becomes a physical cross-linked gel, which can be dissolved in a solvent at the time of manufacture.
  • the manufacturing method can be applied.
  • glycerin is used in addition to ethylene glycol, the main chains of the polyurethane resin are chemically cross-linked.
  • the degree of swelling into the electrolyte can be controlled arbitrarily by controlling the molecular weight between the cross-links.
  • the gel-forming polymer is a polyurethane resin
  • the configuration of the gel-forming polymer is not limited to this.
  • a copolymer of polyvinylidene fluoride and hexafluoropropylene (PVdF-HFP) and polyacrylonitrile (PAN) are similarly used as the gel-forming polymer.
  • PVdF-HFP polyvinylidene fluoride and hexafluoropropylene
  • PAN polyacrylonitrile
  • the tensile strength at break is determined by imparting flexibility to the polymer by controlling the molecular weight of the gel-forming polymer or devising the molecular structure as described above. It is possible to adjust.
  • the conductive material include carbon materials such as ketjen black and acetylene black, carbon materials such as graphite and carbon fiber; various carbon nanotubes (CNT), and vapor grown carbon fiber (VGCF).
  • the ratio of the content of the gel-forming polymer and the conductive material contained in the shell part is not particularly limited, but as an example, the content of the conductive material is preferably 2 with respect to 100% by mass of the gel-forming polymer. -30% by volume, more preferably 5-20% by mass. If the content of the conductive material is 10% by volume or more, it is possible to form a sufficient conductive path, which contributes to reduction (inhibition of increase) of the internal resistance of the battery. On the other hand, if the content of the conductive material is 30% by volume or less, it is preferable from the viewpoint that the change in the base material is small. In addition, the value of the ratio of these contents shall be calculated as an average value of the values measured for 50 or more core-shell type electrode active materials.
  • the electrode active material layer of this embodiment is formed by dispersing an active material in the voids of the fibrous resin skeleton base material.
  • “dispersed in the voids of the fibrous resin skeleton substrate” means that the active material exists in the voids of the fibrous resin skeleton substrate over the entire electrode active material layer.
  • the active material may exist uniformly in the voids of the fibrous resin skeleton base material over the entire electrode active material layer, or may exist non-uniformly (for example, the electrode active material layer It may have a concentration gradient in the thickness direction).
  • the content of the fibrous resin skeleton base material is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass with respect to the active material.
  • the content of the fibrous resin skeleton base material is 0.1% by mass or more, the active material can be retained, and when it is 10% by mass or less, the energy density of the battery is not significantly impaired.
  • the electrode active material layer of this embodiment is made of a conductive additive, binder, electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and other additives such as a lithium salt for enhancing ion conductivity, as necessary. Further included.
  • the content of a material that can function as an active material in the electrode active material layer is preferably 85 to 99.5% by mass.
  • Conductive aid refers to an additive blended to improve the conductivity of the active material layer.
  • the conductive auxiliary agent include carbon materials such as carbon black such as ketjen black and acetylene black, graphite, and carbon fiber.
  • the binder has a function of holding the structure of the electrode active material layer and the conductive network by binding the fibrous resin skeleton base material, the active material, the conductive auxiliary agent, and the like.
  • the material used as a binder is not specifically limited, When using for the electrode active material layer containing a negative electrode active material, it is preferable that a water-system binder is included.
  • a water-based binder has high binding power, and it is easy to procure water as a raw material. In addition, water vapor is generated during drying, which greatly reduces capital investment on the production line and reduces environmental impact. There is an advantage that it is possible to reduce the above.
  • the water-based binder refers to a binder using water as a solvent or a dispersion medium, and specifically includes a thermoplastic resin, a polymer having rubber elasticity, a water-soluble polymer, or a mixture thereof.
  • the binder containing water as a dispersion medium refers to a polymer that includes all expressed as latex or emulsion and is emulsified or suspended in water.
  • a polymer latex that is emulsion-polymerized in a system that self-emulsifies.
  • kind a polymer latex that is emulsion-polymerized in a system that self-emulsifies.
  • water-based binders include styrene polymers (styrene-butadiene rubber, styrene-vinyl acetate copolymer, styrene-acrylic copolymer, etc.), acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, (meta )
  • Acrylic polymers polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polymethyl methacrylate (methyl methacrylate rubber), polypropyl methacrylate, polyisopropyl acrylate, polyisopropyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyhexyl acrylate , Polyhexyl methacrylate, polyethylhexyl acrylate, polyethylhexyl methacrylate, polylauryl acrylate, polylauryl methacrylate Relate,
  • the water-based binder may contain at least one rubber-based binder selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and methyl methacrylate rubber from the viewpoint of binding properties. preferable. Furthermore, the water-based binder preferably contains styrene-butadiene rubber because of good binding properties.
  • Water-soluble polymers suitable for use in combination with styrene-butadiene rubber include polyvinyl alcohol and modified products thereof, starch and modified products thereof, cellulose derivatives (such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and salts thereof), polyvinyl Examples include pyrrolidone, polyacrylic acid (salt), or polyethylene glycol. Among them, it is preferable to combine styrene-butadiene rubber and carboxymethyl cellulose (salt) as a binder.
  • the content of the water-based binder is preferably 80 to 100% by weight, preferably 90 to 100% by weight, and preferably 100% by weight with respect to the total amount of the binder.
  • the binder material other than the water-based binder is not particularly limited.
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • polyacrylonitrile polyimide
  • polyamide polyamideimide
  • cellulose carboxymethylcellulose
  • CMC ethylene-vinyl acetate copolymer
  • polyvinyl chloride styrene / butadiene rubber (SBR), isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block Copolymers and their hydrogenated products
  • thermoplastic polymers such as styrene / isoprene / styrene block copolymers and their hydrogenated products
  • PVdF polyvinylidene fluoride
  • PTFE poly Trafluoroethylene
  • FEP tetrafluoroethylene / hexafluoropropylene copolymer
  • PFA tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
  • ETFE ethylene / tetrafluoroethylene copolymer
  • polyvinylidene fluoride, polyimide, styrene / butadiene rubber, carboxymethyl cellulose, polypropylene, polytetrafluoroethylene, polyacrylonitrile, polyamide, and polyamideimide are more preferable.
  • These suitable binders are excellent in heat resistance, have a very wide potential window, are stable at both the positive electrode potential and the negative electrode potential, and can be used for the active material layer. These binders may be used alone or in combination of two.
  • the binder content is not particularly limited as long as it is an amount capable of binding the active material, but is preferably 0.5 to 15% by mass, more preferably 1%, based on the active material. ⁇ 10% by mass.
  • the thickness of the electrode active material layer of the present embodiment is not particularly limited, and conventionally known knowledge about the battery is appropriately referred to, but is preferably 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m. When the thickness of the electrode active material layer is 10 ⁇ m or more, the battery capacity can be sufficiently secured. On the other hand, if the thickness of the electrode active material layer is about 100 ⁇ m or less, it is possible to suppress the occurrence of the problem of an increase in internal resistance due to the difficulty in diffusing lithium ions into the electrode deep part (current collector side).
  • the manufacturing method will not be specifically limited.
  • a fibrous resin skeleton substrate prepared in advance is brought into contact with an active material dispersion in which an active material is dispersed in a predetermined dispersion solvent, and the active material dispersion is permeated into the fibrous resin skeleton substrate.
  • gap of a fibrous resin frame base material is mentioned.
  • the method for producing an electrode active material layer includes a step of bringing an active material dispersion in which an active material is dispersed in a dispersion solvent into contact with a fibrous resin skeleton substrate.
  • the absolute value ( ⁇ SP) of the difference between at least one solubility parameter of the resin constituting the fibrous resin skeleton base material and the solubility parameter of the dispersion solvent is 1.0 to 10, preferably Is 1.0 to 3.0.
  • the solubility parameter (SP value) is generally used as a measure of the solubility of a binary solution or solvent-solute. It is empirically known that the solubility increases as the absolute value of the difference between the solubility parameter values of the two components decreases.
  • the solubility parameter (SP value) of the resin and the solvent is calculated by the Fedors method. In this case, the SP value can be expressed by the following equation. *
  • SP value ( ⁇ ) ( ⁇ H / V) 1/2
  • ⁇ H represents the heat of vaporization (cal)
  • V represents the molar volume (cm 3 ).
  • ⁇ H and V are the sum of the heat of molar evaporation ( ⁇ H) of the atomic group described in “POLYMER ENGINEERING AND SCIENCE, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 151 to 153)”.
  • the total molar volume (V) can be used.
  • the resin in this embodiment may be a single type of non-conductive polymer material or conductive polymer material, or a mixture of two or more types.
  • the mixed form may have the following two forms.
  • the first mixed form is a case where two or more polymer materials are mixed at the molecular level.
  • the resin solubility parameter in this case employs the sum of values obtained by multiplying the solubility parameter of each polymer material by each content ratio (w / w), that is, a value calculated by the following equation.
  • a k (A 1 , A 2 ... A m ) represents the solubility parameter of each polymer material
  • X k (X 1 , X 2 ... X m ) represents each polymer for the entire resin. It represents the content ratio (w / w) of the material
  • m represents the number of types of single polymer materials to be mixed.
  • the second mixed form is a case where different polymer materials are localized (for example, resin fibers made of different polymer materials are mixed).
  • the value of the solubility parameter of the polymer material having the largest content ratio (w / w) is adopted as the solubility parameter of the resin.
  • the solubility parameter of any one of the polymer materials defines the above. As long as is satisfied.
  • the value calculated from the definition of the first mixed form is It is a solubility parameter of “a polymer material having the largest content ratio (w / w)”. Then, according to the definition of the second mixing form, the value of the solubility parameter becomes the solubility parameter of the resin.
  • a single solvent may be used alone, or a mixture of two or more may be used.
  • the solubility parameter of the solvent when the latter two or more kinds of single solvents are combined is the sum of the values obtained by multiplying the solubility parameter of each single solvent by each content ratio (v / v), that is, by the following formula: Use the calculated value.
  • B 1 (B 1 , B 2 ... B n ) represents the solubility parameter of each single solvent
  • Y 1 (Y 1 , Y 2 ... Y n ) represents each single solvent relative to the whole solvent.
  • the content ratio (v / v) of the solvent is represented, and n represents the number of kinds of single solvents to be mixed.
  • the method for bringing the active material dispersion into contact with the fibrous resin skeleton substrate is not particularly limited.
  • a method in which a fibrous resin skeleton base material is put into a container containing an active material dispersion and immersed a method in which the active material dispersion liquid is dropped, applied, sprayed, etc. on the surface of the fibrous resin skeleton base material;
  • Examples include a method in which a fibrous resin skeleton base material is placed on a droplet of an active material dispersion and brought into contact.
  • the active material dispersion liquid can reach the deep part of the fibrous resin skeleton base material only by contacting the active material dispersion liquid and the fibrous resin skeleton base material by capillary action. It can penetrate and disperse the active material in the voids of the substrate.
  • the method for preparing the active material dispersion and the method for producing the fibrous resin skeleton base material are not particularly limited, and can be produced by appropriately referring to known knowledge.
  • the dispersion solvent may be dried as necessary, but when the dispersion solvent can be used as a solvent for the electrolyte, it is dried as it is. It is also possible to use for the manufacturing process of a battery, and it is simpler.
  • a method of forming a sheet by dispersing pre-molded resin fibers and an active material in an appropriate solvent, and applying and drying it may be employed.
  • the nonaqueous electrolyte secondary battery of the present invention includes a positive electrode in which a positive electrode active material layer is formed on the surface of a positive electrode current collector, and a negative electrode in which a negative electrode active material layer is formed on the surface of a negative electrode current collector. And a power generation element including an electrolyte layer interposed between the positive electrode and the negative electrode.
  • a positive electrode active material layer or a negative electrode active material layer is comprised by the above-mentioned electrode active material layer, It is characterized by the above-mentioned.
  • the nonaqueous electrolyte secondary battery of the present invention will be described mainly by taking a bipolar lithium ion secondary battery that can achieve a high output density as an example.
  • FIG. 2 is a cross-sectional view schematically showing a bipolar secondary battery according to an embodiment of the present invention.
  • the bipolar secondary battery 10 shown in FIG. 2 has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a laminate film 29 that is a battery exterior material.
  • the power generation element 21 of the bipolar secondary battery 10 includes a positive electrode active material layer 13 that is electrically coupled to one surface of the current collector 11.
  • a plurality of bipolar electrodes 23 having a negative electrode active material layer 15 electrically coupled to the opposite surface are provided.
  • at least one of the positive electrode active material layer 13 or the negative electrode active material layer 15, preferably the negative electrode active material layer 15, more preferably both the positive electrode active material layer 13 and the negative electrode active material layer 15 are electrodes shown in FIG. Consists of an active material layer.
  • Each bipolar electrode 23 is laminated via the electrolyte layer 17 to form the power generation element 21.
  • the electrolyte layer 17 has a configuration in which an electrolyte is held at the center in the surface direction of a separator as a base material. At this time, the positive electrode active material layer 13 of one bipolar electrode 23 and the negative electrode active material layer 15 of another bipolar electrode 23 adjacent to the one bipolar electrode 23 face each other through the electrolyte layer 17.
  • the bipolar electrodes 23 and the electrolyte layers 17 are alternately stacked. That is, the electrolyte layer 17 is interposed between the positive electrode active material layer 13 of one bipolar electrode 23 and the negative electrode active material layer 15 of another bipolar electrode 23 adjacent to the one bipolar electrode 23. ing.
  • the adjacent positive electrode active material layer 13, electrolyte layer 17, and negative electrode active material layer 15 constitute one unit cell layer 19. Therefore, it can be said that the bipolar secondary battery 10 has a configuration in which the single battery layers 19 are stacked. Further, for the purpose of preventing liquid junction due to leakage of the electrolytic solution from the electrolyte layer 17, a seal portion (insulating layer) 31 is disposed on the outer peripheral portion of the unit cell layer 19.
  • a positive electrode active material layer 13 is formed only on one side of the positive electrode outermost layer current collector 11 a located in the outermost layer of the power generation element 21.
  • the negative electrode active material layer 15 is formed only on one surface of the outermost current collector 11b on the negative electrode side located in the outermost layer of the power generation element 21.
  • a positive electrode current collector plate 25 is disposed adjacent to the outermost layer current collector 11a on the positive electrode side, and this is extended to form a laminate film 29 that is a battery exterior material.
  • the negative electrode current collector plate 27 is disposed so as to be adjacent to the outermost layer current collector 11 b on the negative electrode side, and is similarly extended and led out from the laminate film 29.
  • a seal portion 31 is usually provided around each single cell layer 19.
  • the purpose of the seal portion 31 is to prevent the adjacent current collectors 11 in the battery from coming into contact with each other and a short circuit caused by a slight irregularity at the end of the unit cell layer 19 in the power generation element 21. Provided. By installing such a seal portion 31, long-term reliability and safety are ensured, and a high-quality bipolar secondary battery 10 can be provided.
  • the number of times the single battery layer 19 is stacked is adjusted according to the desired voltage. Further, in the bipolar secondary battery 10, the number of stacking of the single battery layers 19 may be reduced if a sufficient output can be secured even if the thickness of the battery is made as thin as possible. Even in the bipolar secondary battery 10, in order to prevent external impact and environmental degradation during use, the power generation element 21 is sealed under reduced pressure in a laminate film 29 that is a battery exterior material, and the positive electrode current collector plate 25 and the negative electrode current collector 25. A structure in which the electric plate 27 is taken out of the laminate film 29 is preferable.
  • the embodiment of the present invention has been described by taking a bipolar secondary battery as an example, but the type of the non-aqueous electrolyte secondary battery to which the present invention can be applied is not particularly limited, and a single cell in the power generation element
  • the present invention can be applied to any conventionally known nonaqueous electrolyte secondary battery such as a so-called parallel stacked secondary battery of a type in which layers are connected in parallel.
  • main components of the bipolar secondary battery of this embodiment will be described.
  • the current collector has a function of mediating transfer of electrons from one surface in contact with the positive electrode active material layer to the other surface in contact with the negative electrode active material layer.
  • a metal and resin which has electroconductivity can be employ
  • a resin layer having conductivity it is preferable to employ.
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, and copper.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
  • covered on the metal surface may be sufficient.
  • aluminum, stainless steel, copper, and nickel are preferable from the viewpoints of electronic conductivity, battery operating potential, and adhesion of the negative electrode active material by sputtering to the current collector.
  • the latter conductive resin includes a resin in which a conductive filler is added to a conductive polymer material or a non-conductive polymer material as required.
  • the conductive polymer material include polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene, polyphenylene vinylene, polyacrylonitrile, and polyoxadiazole. Since such a conductive polymer material has sufficient conductivity without adding a conductive filler, it is advantageous in terms of facilitating the manufacturing process or reducing the weight of the current collector.
  • Non-conductive polymer materials include, for example, polyethylene (PE; high density polyethylene (HDPE), low density polyethylene (LDPE), etc.), polypropylene (PP), polyethylene terephthalate (PET), polyether nitrile (PEN), polyimide (PI), polyamideimide (PAI), polyamide (PA), polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR), polyacrylonitrile (PAN), polymethyl acrylate (PMA), polymethyl methacrylate (PMMA) , Polyvinyl chloride (PVC), polyvinylidene fluoride (PVdF), or polystyrene (PS).
  • PE polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PEN polyether nitrile
  • PI polyimide
  • PAI polyamideimide
  • PA polyamide
  • PTFE polytetraflu
  • a conductive filler may be added to the conductive polymer material or the non-conductive polymer material as necessary.
  • a conductive filler is inevitably necessary to impart conductivity to the resin.
  • the conductive filler can be used without particular limitation as long as it has a conductivity.
  • metals, conductive carbon, etc. are mentioned as a material excellent in electroconductivity, electric potential resistance, or lithium ion barrier
  • the metal is not particularly limited, but at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, Sb, and K, or these metals It is preferable to contain an alloy or metal oxide containing.
  • it includes at least one selected from the group consisting of acetylene black, vulcan, black pearl, carbon nanofiber, ketjen black, carbon nanotube, carbon nanohorn, carbon nanoballoon, and fullerene.
  • the amount of the conductive filler added is not particularly limited as long as it is an amount capable of imparting sufficient conductivity to the current collector, and is generally about 5 to 35% by mass.
  • the current collector of this embodiment may have a single-layer structure made of a single material, or may have a laminated structure in which layers made of these materials are appropriately combined. From the viewpoint of reducing the weight of the current collector, it is preferable to include a conductive resin layer made of at least a conductive resin. Further, from the viewpoint of blocking the movement of lithium ions between the unit cell layers, a metal layer may be provided on a part of the current collector.
  • the electrolyte used for the electrolyte layer of the present embodiment is not particularly limited, but from the viewpoint of ensuring the ionic conductivity of the electrode active material layer for a non-aqueous electrolyte secondary battery described above, a liquid electrolyte, a gel polymer electrolyte, or an ion A liquid electrolyte is used.
  • the liquid electrolyte functions as a lithium ion carrier.
  • the liquid electrolyte constituting the electrolytic solution layer has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer.
  • organic solvent include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl methyl carbonate ethyl methyl carbonate.
  • Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF such 6, LiCF 3 SO 3
  • a compound that can be added to the active material layer of the electrode can be similarly employed.
  • the liquid electrolyte may further contain additives other than the components described above.
  • additives include, for example, vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate, phenyl vinylene carbonate, diphenyl vinylene carbonate, ethyl vinylene carbonate, diethyl vinylene carbonate, vinyl ethylene carbonate, 1,2-divinyl ethylene carbonate.
  • vinylene carbonate, methyl vinylene carbonate, and vinyl ethylene carbonate are preferable, and vinylene carbonate and vinyl ethylene carbonate are more preferable.
  • These cyclic carbonates may be used alone or in combination of two or more.
  • the gel polymer electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer (host polymer) made of an ion conductive polymer.
  • a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and the ion conductivity between the layers is easily cut off.
  • ion conductive polymer used as the matrix polymer (host polymer) examples include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene ( PVdF-HEP), poly (methyl methacrylate (PMMA), and copolymers thereof.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEG polyethylene glycol
  • PAN polyacrylonitrile
  • PVdF-HEP polyvinylidene fluoride-hexafluoropropylene
  • PMMA methyl methacrylate
  • the matrix polymer of the gel polymer electrolyte can express excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be performed.
  • the ionic liquid electrolyte is a ionic liquid in which a lithium salt is dissolved.
  • an ionic liquid is a salt comprised only from a cation and an anion, and means a series of compounds which are liquid at normal temperature.
  • the cation component constituting the ionic liquid is substituted or unsubstituted imidazolium ion, substituted or unsubstituted pyridinium ion, substituted or unsubstituted pyrrolium ion, substituted or unsubstituted Pyrazolium ion, substituted or unsubstituted pyrrolinium ion, substituted or unsubstituted pyrrolidinium ion, substituted or unsubstituted piperidinium ion, substituted or unsubstituted tria It is preferably at least one selected from the group consisting of dinium ions and substituted or unsubstituted ammonium ions.
  • anion component constituting the ionic liquid include halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion, nitrate ion (NO 3 ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), Hexafluorophosphate ion (PF 6 ⁇ ), (FSO 2 ) 2 N ⁇ , AlCl 3 ⁇ , lactate ion, acetate ion (CH 3 COO ⁇ ), trifluoroacetate ion (CF 3 COO ⁇ ), methanesulfone Acid ion (CH 3 SO 3 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), bis (trifluoromethanesulfonyl) imide ion ((CF 3 SO 2 ) 2 N ⁇ ), bis (pentafluoroethylsulfonyl
  • preferable ionic liquids include 1-methyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide and N-methyl-N-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide. As for these ionic liquids, only 1 type may be used independently and 2 or more types may be used together.
  • the lithium salt used for the ionic liquid electrolyte is the same as the lithium salt used for the liquid electrolyte described above.
  • the concentration of the lithium salt is preferably 0.1 to 2.0M, and more preferably 0.8 to 1.2M.
  • the following additives may be added to the ionic liquid.
  • charge / discharge characteristics and cycle characteristics at a high rate can be further improved.
  • Specific examples of the additive include, for example, vinylene carbonate, ethylene carbonate, propylene carbonate, ⁇ -butyl lactone, ⁇ -valerolactone, methyl diglyme, sulfolane, trimethyl phosphate, triethyl phosphate, methoxymethyl ethyl carbonate, Examples thereof include fluorinated ethylene carbonate. These may be used alone or in combination of two or more.
  • the amount of the additive used is preferably 0.5 to 10% by mass, more preferably 0.5 to 5% by mass, based on the ionic liquid.
  • the difference in solubility parameter between at least one resin constituting the fibrous resin skeleton base material contained in the active material layer and at least one liquid component contained in the electrolyte layer The absolute value ( ⁇ SP) is preferably 1.0 to 10.
  • the ⁇ SP is more preferably 1.0 to 3.0.
  • the “liquid component contained in the electrolyte layer” refers to a substance that is liquid at room temperature among substances constituting the electrolyte, specifically, an organic substance contained in the liquid electrolyte described above. It means solvent, ionic liquid, etc.
  • the solubility parameter of the liquid component when the liquid component is a mixture of two or more single components is the same as the content of each single component (v) as in the case of the dispersion solvent described above. A value calculated from the sum of values multiplied by / v) is adopted.
  • the fibrous resin skeleton base material does not swell excessively due to the liquid component contained in the electrolyte layer, so that it is possible to suppress a decrease in capacity due to insufficient electrolyte.
  • the fibrous resin skeleton base material and the liquid component contained in the electrolyte layer are likely to be compatible with each other, so that the lithium ion conductivity in the active material is improved.
  • a separator may be used for the electrolyte layer.
  • the separator has a function of holding an electrolyte and ensuring lithium ion conductivity between the positive electrode and the negative electrode, and a function as a partition wall between the positive electrode and the negative electrode.
  • a separator it is preferable to use a separator.
  • separator examples include a separator made of a porous sheet made of a polymer or fiber that absorbs and holds the electrolyte and a nonwoven fabric separator.
  • a microporous (microporous film) can be used as the separator of the porous sheet made of polymer or fiber.
  • the porous sheet made of the polymer or fiber include polyolefins such as polyethylene (PE) and polypropylene (PP); a laminate in which a plurality of these are laminated (for example, three layers of PP / PE / PP) And a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • PE polyethylene
  • PP polypropylene
  • a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • the thickness of the microporous (microporous membrane) separator cannot be uniquely defined because it varies depending on the intended use. For example, in applications such as secondary batteries for driving motors such as electric vehicles (EV), hybrid electric vehicles (HEV), and fuel cell vehicles (FCV), it is 4 to 60 ⁇ m in a single layer or multiple layers. Is desirable.
  • the fine pore diameter of the microporous (microporous membrane) separator is desirably 1 ⁇ m or less (usually a pore diameter of about several tens of nm).
  • nonwoven fabric separator cotton, rayon, acetate, nylon, polyester; polyolefins such as PP and PE; conventionally known ones such as polyimide and aramid are used alone or in combination.
  • the bulk density of the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated polymer gel electrolyte.
  • the thickness of the nonwoven fabric separator may be the same as that of the electrolyte layer, and is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • the separator is preferably a separator in which a heat-resistant insulating layer is laminated on a porous substrate (a separator with a heat-resistant insulating layer).
  • the heat resistant insulating layer is a ceramic layer containing inorganic particles and a binder.
  • a highly heat-resistant separator having a melting point or a heat softening point of 150 ° C. or higher, preferably 200 ° C. or higher is used.
  • the separator is less likely to curl in the battery manufacturing process due to the effect of suppressing thermal shrinkage and high mechanical strength.
  • the inorganic particles in the heat resistant insulating layer contribute to the mechanical strength and heat shrinkage suppressing effect of the heat resistant insulating layer.
  • the material used as the inorganic particles is not particularly limited. Examples thereof include silicon, aluminum, zirconium, titanium oxides (SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 ), hydroxides and nitrides, and composites thereof. These inorganic particles may be derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine and mica, or may be artificially produced. Moreover, only 1 type may be used individually for these inorganic particles, and 2 or more types may be used together. Of these, silica (SiO 2 ) or alumina (Al 2 O 3 ) is preferably used, and alumina (Al 2 O 3 ) is more preferably used from the viewpoint of cost.
  • the basis weight of the heat-resistant particles is not particularly limited, but is preferably 5 to 15 g / m 2 . If it is this range, sufficient ion conductivity will be acquired and it is preferable at the point which maintains heat resistant strength.
  • the binder in the heat-resistant insulating layer has a role of adhering the inorganic particles and the inorganic particles to the resin porous substrate layer.
  • the heat resistant insulating layer is stably formed, and peeling between the porous substrate layer and the heat resistant insulating layer is prevented.
  • the binder used for the heat-resistant insulating layer is not particularly limited.
  • a compound such as butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), or methyl acrylate can be used as the binder.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVF polyvinyl fluoride
  • methyl acrylate methyl acrylate
  • PVDF polyvinylidene fluoride
  • these compounds only 1 type may be used independently and 2 or more types may be used together.
  • the binder content in the heat-resistant insulating layer is preferably 2 to 20% by weight with respect to 100% by weight of the heat-resistant insulating layer.
  • the binder content is 2% by weight or more, the peel strength between the heat-resistant insulating layer and the porous substrate layer can be increased, and the vibration resistance of the separator can be improved.
  • the binder content is 20% by weight or less, the gap between the inorganic particles is appropriately maintained, so that sufficient lithium ion conductivity can be ensured.
  • the thermal contraction rate of the separator with a heat-resistant insulating layer is preferably 10% or less for both MD and TD after holding for 1 hour at 150 ° C. and 2 gf / cm 2 .
  • the material which comprises a current collector plate (25, 27) is not restrict
  • a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable.
  • the same material may be used for the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25, and different materials may be used.
  • the seal portion (insulating layer) has a function of preventing contact between current collectors and a short circuit at the end of the single cell layer.
  • acrylic resin, urethane resin, epoxy resin, polyethylene resin, polypropylene resin, polyimide resin, rubber (ethylene-propylene-diene rubber: EPDM), and the like can be used.
  • an isocyanate-based adhesive an acrylic resin-based adhesive, a cyanoacrylate-based adhesive, or the like may be used, and a hot-melt adhesive (urethane resin, polyamide resin, polyolefin resin) or the like may be used.
  • a hot-melt adhesive urethane resin, polyamide resin, polyolefin resin
  • polyethylene resin and polypropylene resin are preferably used as the constituent material of the insulating layer, and amorphous polypropylene resin is mainly used. It is preferable to use a resin obtained by copolymerizing ethylene, propylene and butene as components.
  • the battery outer case 29 a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
  • a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto.
  • a laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
  • the exterior body is more preferably an aluminate laminate.
  • the positive electrode active material layer or the negative electrode active material layer is configured using the above-described electrode active material layer, so that even if an active material having a large battery capacity is used, Stress due to shrinkage is relieved, and cycle characteristics of the battery can be improved. Therefore, the bipolar secondary battery of this embodiment is suitably used as a driving power source for EVs and HEVs.
  • FIG. 3 is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of the secondary battery.
  • the flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive electrode tab 58 and a negative electrode tab 59 for taking out electric power are drawn out from both sides thereof.
  • the power generation element 57 is wrapped by a battery exterior material (laminate film 52) of the lithium ion secondary battery 50, and the periphery thereof is heat-sealed.
  • the power generation element 57 pulls out the positive electrode tab 58 and the negative electrode tab 59 to the outside. Sealed.
  • the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery 10 illustrated in FIG. 2 described above.
  • the power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 15, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 13.
  • the lithium ion secondary battery is not limited to a stacked flat shape.
  • the wound lithium ion secondary battery may have a cylindrical shape, or may have a shape that is a flattened rectangular shape by deforming such a cylindrical shape.
  • a laminate film may be used for the exterior material, and the conventional cylindrical can (metal can) may be used, for example, It does not restrict
  • the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.
  • the tabs 58 and 59 shown in FIG. 3 are not particularly limited.
  • the positive electrode tab 58 and the negative electrode tab 59 may be drawn out from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, as shown in FIG. It is not limited to.
  • a terminal may be formed using a cylindrical can (metal can).
  • the battery storage space is about 170L. Since auxiliary devices such as cells and charge / discharge control devices are stored in this space, the storage efficiency of a normal cell is about 50%. The efficiency of loading cells into this space is a factor that governs the cruising range of electric vehicles. If the size of the single cell is reduced, the loading efficiency is impaired, so that the cruising distance cannot be secured.
  • the battery structure in which the power generation element is covered with the exterior body is preferably large.
  • the length of the short side of the laminated cell battery is preferably 100 mm or more. Such a large battery can be used for vehicle applications.
  • the length of the short side of the laminated cell battery refers to the side having the shortest length.
  • the upper limit of the short side length is not particularly limited, but is usually 400 mm or less.
  • volume energy density and rated discharge capacity In a general electric vehicle, a travel distance (cruising range) by a single charge is 100 km. Considering such a cruising distance, the volume energy density of the battery is preferably 157 Wh / L or more, and the rated capacity is preferably 20 Wh or more.
  • the ratio of the battery area (projected area of the battery including the battery outer package) to the rated capacity is 5 cm 2 / Ah or more, and the rated capacity is 3 Ah or more.
  • the battery area per unit capacity is large. Therefore, the problem of deterioration of battery characteristics (cycle characteristics) caused by the collapse of the crystal structure accompanying expansion and contraction of the active material is more likely to become apparent.
  • the nonaqueous electrolyte secondary battery according to the present embodiment is a battery having a large size as described above, because the merit due to the expression of the effects of the present invention is greater.
  • the aspect ratio of the rectangular electrode is preferably 1 to 3, and more preferably 1 to 2.
  • the electrode aspect ratio is defined as the aspect ratio of the rectangular positive electrode active material layer.
  • the assembled battery is configured by connecting a plurality of batteries. Specifically, at least two or more are used, and are configured by serialization, parallelization, or both. Capacitance and voltage can be freely adjusted by paralleling in series.
  • a small assembled battery that can be attached and detached by connecting a plurality of batteries in series or in parallel. Then, a plurality of small assembled batteries that can be attached and detached are connected in series or in parallel to provide a large capacity and large capacity suitable for vehicle drive power supplies and auxiliary power supplies that require high volume energy density and high volume output density.
  • An assembled battery having an output can also be formed. How many batteries are connected to make an assembled battery, and how many small assembled batteries are stacked to make a large-capacity assembled battery depends on the battery capacity of the mounted vehicle (electric vehicle) It may be determined according to the output.
  • the nonaqueous electrolyte secondary battery of the present invention maintains a discharge capacity even when used for a long period of time, and has good cycle characteristics. Furthermore, the volume energy density is high. Vehicle applications such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles require higher capacity, larger size, and longer life than electric and portable electronic devices. . Therefore, the nonaqueous electrolyte secondary battery can be suitably used as a vehicle power source, for example, a vehicle driving power source or an auxiliary power source.
  • a battery or an assembled battery formed by combining a plurality of these batteries can be mounted on the vehicle.
  • a plug-in hybrid electric vehicle having a long EV mileage or an electric vehicle having a long charge mileage can be formed by mounting such a battery.
  • a car a hybrid car, a fuel cell car, an electric car (four-wheeled vehicles (passenger cars, trucks, buses, commercial vehicles, light cars, etc.) This is because it can be used for motorcycles (including motorcycles) and tricycles) to provide a long-life and highly reliable automobile.
  • the application is not limited to automobiles.
  • it can be applied to various power sources for moving vehicles such as other vehicles, for example, trains, and power sources for mounting such as uninterruptible power supplies. It is also possible to use as.
  • Example 1 ⁇ Manufacture of electrode active material layer for non-aqueous electrolyte secondary battery> 30 parts by mass of graphite (particle size 20 ⁇ m) as an active material and 70 parts by mass of diethyl carbonate (DEC, solubility parameter 8.8) as a dispersion solvent were mixed to prepare an active material dispersion (solid content ratio 30% by mass).
  • graphite particle size 20 ⁇ m
  • DEC diethyl carbonate
  • solubility parameter 8.8 solubility parameter 8.8
  • Nonwoven film of polyethylene terephthalate (PET, solubility parameter 11.3) as a fibrous resin skeleton substrate size 5.0 cm ⁇ 5.0 cm, thickness 20 ⁇ m, fiber diameter 0.8 ⁇ m ⁇ 0.1 ⁇ m, air permeability 43 cm 3 / cm 2 ⁇ sec, pore diameter 300 ⁇ m, porosity 98%).
  • the PET nonwoven fabric film was placed on 50 mL of the active material dispersion, and the active material dispersion was infiltrated into the PET nonwoven film.
  • an electrode active material layer for a non-aqueous electrolyte secondary battery in which graphite was dispersed in the voids of the PET fiber was manufactured.
  • the obtained electrode active material layer for a non-aqueous electrolyte secondary battery contained 5% by mass of a fibrous resin skeleton base material with respect to the active material.
  • Example 2 An electrode active material layer for a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that ethyl acetate (solubility parameter 9.0) was used as a dispersion solvent.
  • Example 3 An electrode active material layer for a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that methyl ethyl ketone (MEK, solubility parameter 9.3) was used as a dispersion solvent.
  • MEK methyl ethyl ketone
  • Example 4 An electrode active material layer for a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that acetone (solubility parameter 10.0) was used as a dispersion solvent.
  • Example 5 Except for using a 3: 7 (volume ratio) mixed solvent (solubility parameter 9.3) of ethylene carbonate (EC, solubility parameter 10.6) and diethyl carbonate (DEC, solubility parameter 8.8) as a dispersion solvent.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • a non-aqueous electrolyte secondary battery electrode active material layer was produced in the same manner as in Example 1.
  • the solubility parameter of the mixed solvent was calculated as follows.
  • Example 6 An electrode active material layer for a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that methanol (solubility parameter 14.5) was used as the dispersion solvent.
  • the active material dispersion liquid penetrated into the fibrous resin skeleton substrate, and the active material was dispersed in the voids of the fibrous resin skeleton substrate.
  • the absolute value ⁇ SP of the difference between the SP value of the dispersion solvent and the SP value of the resin constituting the fibrous resin skeleton base material is set to 1.0 to 10, so that the base material does not swell excessively. It was thought that this was due to the fact that the active material dispersion became easy to penetrate into the base material.
  • 1 electrode active material layer for non-aqueous electrolyte secondary battery 3 Fibrous resin skeleton substrate, 5 negative electrode active material, 10 Bipolar secondary battery, 11 Current collector, 13 positive electrode active material layer, 15 negative electrode active material layer, 11a The outermost layer current collector on the positive electrode side, 11b The outermost layer current collector on the negative electrode side, 17 electrolyte layer, 19 cell layer, 21, 57 power generation element, 23 Bipolar electrode, 25 positive current collector, 27 negative current collector, 29, 52 Laminate film, 31 seal part, 50 lithium ion secondary battery, 58 positive electrode tab, 59 Negative electrode tab.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

　La présente invention concerne un moyen permettant de soulager les contraintes dues à l'expansion/la contraction de la substance active d'une électrode, et d'améliorer les caractéristiques de cycle d'une batterie. Cette couche de substance active d'électrode pour batterie secondaire à électrolyte non aqueux est caractérisée en ce qu'elle comprend un matériau de base à ossature en résine fibreuse et une substance active, et en ce qu'elle est obtenue par dispersion de la substance active dans des vides dans le matériau de base à ossature en résine fibreuse.
PCT/JP2014/076595 2013-10-07 2014-10-03 Couche de substance active d'électrode pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux utilisant cette couche WO2015053199A1 (fr)

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CN113106568B (zh) * 2021-04-06 2022-06-03 电子科技大学 一种Ag浓度梯度三维骨架及其制备方法和应用

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