WO2016104679A1 - 非水電解質二次電池とその製造方法 - Google Patents
非水電解質二次電池とその製造方法 Download PDFInfo
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- WO2016104679A1 WO2016104679A1 PCT/JP2015/086179 JP2015086179W WO2016104679A1 WO 2016104679 A1 WO2016104679 A1 WO 2016104679A1 JP 2015086179 W JP2015086179 W JP 2015086179W WO 2016104679 A1 WO2016104679 A1 WO 2016104679A1
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- 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
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- H—ELECTRICITY
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- 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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a non-aqueous electrolyte secondary battery and a manufacturing method thereof.
- a bipolar secondary battery has been proposed as a battery that can save current collecting tabs of a single battery cell, a bus bar for connection between single cells, etc., and has a high volumetric efficiency and is suitable for in-vehicle use.
- a bipolar secondary battery (also called a bipolar secondary battery) uses a bipolar electrode in which a positive electrode is formed on one surface of a current collector and a negative electrode is formed on the other surface. A plurality of the bipolar electrodes are laminated so that the positive electrode and the negative electrode face each other through a separator including an electrolyte layer.
- one battery cell (unit cell) is constituted by the positive electrode, the negative electrode, and the separator (electrolyte layer) between the current collector and the current collector. Furthermore, it has been proposed to use a resin in which a conductive filler is dispersed in a current collector for higher performance.
- Patent Document 1 discloses means for increasing the energy density of the battery by increasing the film thickness of the electrode, thereby reducing the relative proportion of the current collector and the separator.
- the conventional method of applying the active material slurry to the current collector may make it difficult to produce the electrode itself.
- the present inventors diligently studied to solve the above problems.
- the component member of the electrode has a first main surface that contacts the electrolyte layer side and a second main surface that contacts the current collector side, and comes into contact with the active material from the first main surface to the second main surface.
- a conductive member forming a conductive path that electrically connects the surface, a thick electrode could be produced.
- At least one of the electrodes includes a conductive member and an active material coated with a coating agent containing a coating resin and a conductive auxiliary agent, and the conductive member electrically contacts both active surfaces while contacting the active material.
- a non-aqueous electrolyte secondary battery having a conductive path connected to each other is provided.
- the thickness of the electrode is increased.
- a water electrolyte secondary battery can be realized.
- the electrolyte of the nonaqueous electrolyte secondary battery of the present invention is gelled. Therefore, even if vibration is applied, the influence is reduced by gelation, and the constituent members of the electrode can be stably held, so that the cycle characteristics are also improved.
- the power generation element includes: two electrodes having different polarities, each having an active material layer formed on a current collector; and an electrolyte layer disposed between the electrodes.
- a nonaqueous electrolyte secondary battery wherein at least one of the active material layers of the two electrodes having different polarities includes a conductive member and an active material made of an electron conductive material, and the active material layer is the electrolyte layer A first main surface that contacts the side and a second main surface that contacts the current collector side, and at least a part of the conductive member is electrically connected from the first main surface to the second main surface.
- the conductive path is in contact with the active material around the conductive path, and at least a part of the surface of the active material includes a coating resin and a conductive auxiliary agent.
- the two electrodes having different polarities are coated with a coating material containing Or the electrolyte contained in the electrolyte layer, a gel electrolyte, a non-aqueous electrolyte secondary battery is provided.
- the thickness of the electrode is increased.
- a water electrolyte secondary battery can be provided.
- the electrolyte solution of the nonaqueous electrolyte secondary battery of the present invention is gelled. Due to the presence of the gelled electrolyte, even if some force is locally applied to the electrode, the electrode reaction becomes uniform without being deformed, deterioration can be suppressed, and cycle characteristics can be improved.
- bipolar lithium ion secondary battery may be simply referred to as “bipolar secondary battery”, and the bipolar lithium ion secondary battery electrode may be simply referred to as “bipolar electrode”.
- active material may mean either a positive electrode active material or a negative electrode active material, or may mean both. The same applies to the “active material layer”. Those skilled in the art can reasonably interpret these.
- FIG. 1 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. 1 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.
- 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.
- 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 sandwiched 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. Has been.
- 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.
- a seal portion (insulating layer) 31 is disposed on the outer peripheral portion of the unit cell layer 19. Thereby, a liquid junction due to leakage of the electrolytic solution from the electrolyte layer 17 is prevented, the adjacent current collectors 11 in the battery are in contact with each other, a slight irregularity of the end portion of the unit cell layer 19 in the power generation element 21, etc.
- 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 so as to be adjacent to the outermost layer current collector 11a on the positive electrode side, and this is extended to form a laminate film 29 which 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.
- the number of times the single battery layer 19 is stacked is adjusted according to the desired voltage.
- 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 battery to which the present invention is applicable is not particularly limited, and a single cell layer is provided 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 battery of a type connected in parallel.
- 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
- 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 viewpoint of electronic conductivity and battery operating potential.
- 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 includes at least one metal selected from the group consisting of Ni, Ti, Al, Cu, Pt, Fe, Cr, Sn, Zn, In, and Sb, or these metals. It preferably contains an alloy or metal oxide.
- 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 weight.
- 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. 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.
- At least one of the positive electrode active material layer and the negative electrode active material layer includes a conductive member and an active material made of an electron conductive material.
- at least a part of the surface of the active material is coated with a coating agent containing a coating resin and a conductive additive.
- the active material layer has a first main surface that contacts the electrolyte layer side and a second main surface that contacts the current collector side. At least a part of the conductive member forms a conductive path that electrically connects the first main surface to the second main surface.
- the conductive member is an example of a conductive fiber constituting a part of a nonwoven fabric, an example of a conductive fiber constituting a part of a woven fabric or a knitted fabric, the first main surface and the second surface.
- conductive fibers that exist discretely between the main surfaces
- examples are conductive resins that constitute a part of the foamed resin.
- the conductive member is a conductive fiber constituting a part of the nonwoven fabric.
- FIG. 2 is a cross-sectional view schematically showing an enlarged part indicated by a circle in FIG.
- the single battery layer 19 is sandwiched between two current collectors 11.
- the positive electrode active material layer 13 is in the form of a sheet having a predetermined thickness t1, and includes a first main surface 111 disposed on the electrolyte layer 17 side and a second main surface 121 disposed on the current collector 11 side. ing.
- the positive electrode active material layer 13 includes a positive electrode active material 14.
- the positive electrode active material 14 is covered with a coating agent, which will be described later.
- the negative electrode active material layer 15 also has a sheet shape having a predetermined thickness t2, and includes a first main surface 211 disposed on the electrolyte layer 17 side and a second main surface 221 disposed on the current collector 11 side. I have.
- the negative electrode active material layer 15 contains a negative electrode active material 24. In this embodiment, the negative electrode active material 24 is coated with a coating agent, which will be described later.
- the thickness t1 of the positive electrode active material layer 13 and the thickness t2 of the negative electrode active material layer 15 are preferably independently 150 to 1500 ⁇ m.
- the thickness t1 is more preferably 200 to 950 ⁇ m, and further preferably 250 to 900 ⁇ m.
- the thickness t2 is more preferably 200 to 950 ⁇ m, and further preferably 250 to 900 ⁇ m. According to the characteristic structure of the present invention, such a thick electrode can be realized, which is effective in improving the energy density.
- FIG. 3 is a cross-sectional view schematically showing only the positive electrode active material layer of FIG.
- the positive electrode active material layer 100 includes the first main surface 111 and the second main surface 121 (not shown) as described above. And between the 1st main surface 111 and the 2nd main surface 121, the conductive fiber 131 as a conductive member and the positive electrode active material 14 as an active material are contained.
- the conductive member is a conductive fiber 131 constituting a part of the nonwoven fabric. Since there are many voids in the nonwoven fabric, an electrode can be formed by filling the voids with the active material 14. The filling of the coating active material into the voids will be described in detail below.
- one end of some of the fibers reaches the first main surface 111, and the other end reaches the second main surface 121. Therefore, at least a part of the conductive fiber 131 forms a conductive path that electrically connects the first main surface 111 to the second main surface 121.
- conductive fibers 131 are entangled between the first main surface 111 and the second main surface 121, but a plurality of conductive fibers 131 are in contact with each other from the first main surface 111. Even when the second main surface 121 is continuously connected, it can be said that the conductive fibers form a conductive path that electrically connects the first main surface 111 to the second main surface 121.
- FIG. 3 shows an example of the conductive fiber 131 corresponding to the conductive path that electrically connects the first main surface 111 to the second main surface 121.
- the fiber shown as the conductive fiber 131a is an example in which one conductive fiber is a conductive path, and the two fibers shown as the conductive fiber 131b are a conductive path by contacting two conductive fibers. This is an example.
- Examples of conductive fibers include carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, conductive fibers obtained by uniformly dispersing highly conductive metal and graphite in synthetic fibers, and metals such as stainless steel. Examples thereof include fiberized metal fibers, conductive fibers obtained by coating the surfaces of organic fibers with metal, and conductive fibers obtained by coating the surfaces of organic fibers with a resin containing a conductive substance. Among these conductive fibers, carbon fibers are preferable.
- the electric conductivity of the conductive member is preferably 50 mS / cm or more.
- the electrical conductivity is obtained by measuring the volume resistivity in accordance with JIS R 7609 (2007) “Method for obtaining volume resistivity” and taking the reciprocal of the volume resistivity.
- the electrical conductivity is 50 mS / cm or more, the resistance when forming a conductive path that electrically connects the first main surface 111 to the second main surface 121 is small, and the distance from the current collector is long. This is preferable because electrons move more smoothly from the active material.
- the average fiber diameter of the conductive fibers is preferably 0.1 to 20 ⁇ m.
- the average fiber diameter of the conductive fibers can be measured by SEM observation.
- the diameter near the center is measured for each of the 10 arbitrary fibers existing in the 30 ⁇ m square field of view, and this measurement is performed for the three fields of view. Measured value.
- the fiber length of the conductive fiber is not particularly limited.
- the active material is a coated active material in which at least a part of the surface is coated with a coating 151 containing a coating resin and a conductive additive 16. Details will be described later.
- the conductive path by the conductive fiber 131 is in contact with the positive electrode active material 14 around the conductive path.
- the conductive path is made of a conductive member that is an electron conductive material, electrons can smoothly reach the current collector.
- the active material is a coated active material. However, even when the coating agent is in contact with the conductive path, it can be considered that the conductive path is in contact with the active material.
- the conductive auxiliary agent 16 is selected from conductive materials. Details of the conductive assistant will be described later.
- the conductive additive 16 is included in the coating material 151, but the conductive additive 16 may be in contact with the positive electrode active material 14.
- the conductive auxiliary agent 16 is contained in the coating material 151 or is in contact with the positive electrode active material 14, the electron conductivity from the positive electrode active material 14 to the conductive path can be further increased.
- the positive electrode has been described as an example.
- a negative electrode active material can be used as the active material instead of the positive electrode active material. Details of the negative electrode active material will also be described later.
- FIG. 4 is a cross-sectional view schematically showing another example of the positive electrode active material layer.
- the conductive member is a conductive fiber 113 constituting a part of the fabric.
- the woven fabric is composed of warp yarn 113a and weft yarn 113b made of conductive fibers.
- 4 has the same structure as the positive electrode active material layer 100 shown in FIG. 2 except that the cloth-like fiber structure corresponding to the nonwoven fabric in FIG. 3 is a woven fabric.
- the weaving method of the woven fabric is not particularly limited, and a woven fabric woven with a plain weave, a twill weave, a satin weave, a pile weave, or the like can be used. Further, a knitted fabric made of conductive fibers may be used instead of the woven fabric.
- the method of knitting the knitted fabric is not particularly limited, and a knitted fabric knitted by a flat knitting, a vertical knitting, a circular knitting or the like can be used.
- Woven fabrics and knitted fabrics, like non-woven fabrics have many voids between the conductive fibers that make up the woven fabrics and knitted fabrics, so an electrode (active material layer) is formed by filling the voids with a coated active material. Can be made.
- the conductive fibers 113 reach the first main surface 111, and some of the other fibers reach the second main surface 121. Accordingly, at least a part of the conductive fiber 113 forms a conductive path that electrically connects the first main surface 111 to the second main surface 121.
- a preferable conductive fiber type and active material type are the same as those shown in FIG. 2, and thus detailed description thereof is omitted.
- it can also be set as a negative electrode by making an active material into a negative electrode active material.
- FIG. 5 is a cross-sectional view schematically showing another example of the positive electrode active material layer.
- the conductive member is a conductive fiber 213 that exists discretely between the first main surface 111 and the second main surface 121.
- the conductive fiber 213 is not a part of a structure made of conductive fibers such as the nonwoven fabric, woven fabric or knitted fabric shown in FIGS.
- this form is manufactured using a slurry containing conductive fibers and a coated active material, and in the active material layer It can be said that the conductive fibers are discretely present, but the gap between the fibers is not filled with the coating active material.
- the conductive fibers 213 At least some of the fibers reach the first main surface 111, and some of the other fibers reach the second main surface 121. Therefore, at least a part of the conductive fiber 213 forms a conductive path that electrically connects the first main surface 111 to the second main surface 121.
- the fiber shown as the conductive fiber 213a is an example in which one conductive fiber is a conductive path, and the two fibers shown as the conductive fiber 213b are conductive when the two conductive fibers come into contact with each other. This is an example of a passage.
- a preferable conductive fiber type and active material type are the same as those shown in FIG. 2, and thus detailed description thereof is omitted.
- it can also be set as a negative electrode by making an active material into a negative electrode active material.
- the conductive fiber as the conductive member and the coated active material may be fixed on the film and loosely maintained so that the shape does not flow. It is preferable that the film is made of a highly conductive material (conductive material) because the film can be used as a current collector, and even if the current collector and the film are brought into contact with each other, the conductivity is not inhibited.
- the film is not shown in FIG. A manufacturing method in which the conductive fiber as the conductive member and the coated active material are fixed on the film will be described in detail later.
- the conductive fiber as the conductive member and the coated active material are fixed by the resin, and the conductive fiber is dispersed in the active material layer. It may be in a state maintained in step (b).
- FIG. 6 is a cross-sectional view schematically showing another example of the positive electrode active material layer.
- the positive electrode active material layer 100 in the form shown in FIG. 6 is different in that the conductive fibers 213 as the conductive member and the positive electrode active material 14 (coating active material) as the active material are fixed by the resin 214.
- the other configuration is the same as that shown in FIG.
- Examples of the resin include vinyl resin, urethane resin, polyester resin, and polyamide resin.
- FIG. 7 is a cross-sectional view schematically showing another example of the positive electrode active material layer.
- the conductive member is a conductive resin 313 that constitutes a part of the foamed resin. Since many voids exist in the foamed resin, an electrode can be formed by filling the voids with a coating active material.
- the resin subjected to the conductive treatment examples include a resin provided with conductivity by forming a conductive thin film on the surface of the resin, a resin provided with conductivity by mixing a conductive filler such as metal or carbon fiber inside the resin, and the like. Can be mentioned.
- the resin itself may be a conductive polymer, or a resin in which conductivity is further imparted to the conductive polymer.
- Examples of methods for forming a conductive thin film on the surface of a resin include metal plating, vapor deposition, and sputtering.
- the conductive resin 313 is continuous from the first main surface 111 to the second main surface 121, and the conductive resin 313 is transferred from the first main surface 111 to the second main surface 121. Conductive passages are formed to electrically connect the above.
- a resin foam is preferable, and examples thereof include polyurethane foam, polystyrene foam, polyethylene foam, and polypropylene foam.
- a foamed resin obtained by plating the surface of the polyurethane foam with a metal such as nickel is preferable.
- the electrical conductivity of the foamed resin containing the conductive resin is preferably 100 mS / cm or more.
- the electrical conductivity of the foamed resin is determined by the four-terminal method.
- the electrical conductivity of the foamed resin including the conductive resin is 100 mS / cm or more, a conductive path that electrically connects the first main surface to the second main surface is formed by the conductive fiber. This is preferable because the electron resistance from the active material is small and the movement of electrons from the active material that is far from the current collector is performed more smoothly.
- it can also be set as a negative electrode by making an active material into a negative electrode active material.
- the volume ratio of the conductive member is 0.1 to 15 vol% based on the volume of the positive electrode active material layer. Is preferred. That is, it is preferable that the volume occupied by the conductive member is relatively small in the positive electrode active material layer. The fact that the volume occupied by the conductive member is small means that a large number of coating active materials are filled in the gaps not occupied by the conductive member. Electrode. In this example, the volume ratio occupied by the conductive member was about 2 vol%.
- the ratio of the volume occupied by the coated active material is 30 to 80 vol% based on the volume of the active material layer.
- the volume ratio occupied by the conductive member was about 46 vol%.
- a method for producing a non-aqueous electrolyte secondary battery includes: two electrodes having different active polarities, each having an active material layer formed on a current collector; and an electrolyte disposed between the electrodes.
- a non-aqueous electrolyte secondary battery having a power generation element comprising: a conductive member made of an electron conductive material and an active material on at least one of the active material layers of the two electrodes having different polarities
- the active material layer has a first main surface that contacts the electrolyte layer side and a second main surface that contacts the current collector side, and at least a part of the conductive member includes the first main surface
- a conductive path electrically connecting from one main surface to the second main surface, wherein the conductive path is in contact with the active material around the conductive path, and the surface of the active material is Coating agent comprising at least a part of a coating resin and a conductive additive
- One aspect of a method for producing an electrode (active material layer) of a nonaqueous electrolyte secondary battery of the present invention includes a conductive member, and has a plurality of voids therein, and includes a first main surface and a second main surface.
- a step of preparing the provided structure a step of applying a slurry containing the coating active material to the first main surface or the second main surface of the structure, and pressurization or decompression to apply the coating active material. Filling the voids in the structure.
- the manufacturing method of the above aspect is suitable for manufacturing the active material layer of the aspect described with reference to FIG. 3, FIG. 4 or FIG.
- a structure including a conductive member and having a plurality of voids therein and having a first main surface and a second main surface is prepared (this is the first main surface and the second main surface of the active material layer). Skeleton).
- a non-woven fabric containing a conductive member made of conductive fibers As the structure, it is preferable to use a non-woven fabric containing a conductive member made of conductive fibers, a woven or knitted fabric containing a conductive member made of conductive fibers, or a foamed resin containing a conductive member made of a conductive resin.
- the details of the non-woven fabric, the woven fabric, the knitted fabric and the foamed resin are the same as those described above, and the detailed description thereof is omitted.
- FIG. 8A and FIG. 8B are process diagrams schematically showing a process of filling the active material in the voids in the structure. The example using a nonwoven fabric as a structure is shown.
- the slurry containing the coating active material is applied to the first main surface or the second main surface of the structure.
- the active material is coated with a coating agent to form a coated active material.
- the description of the method for producing the coated active material will be described later.
- the slurry containing the active material may be a solvent slurry containing a solvent or an electrolyte solution slurry containing an electrolyte solution. Note that the description of the slurry can be similarly applied to other embodiments.
- solvent examples include water, propylene carbonate, 1-methyl-2-pyrrolidone (N-methylpyrrolidone), methyl ethyl ketone, dimethylformamide, dimethylacetamide, N, N-dimethylaminopropylamine and tetrahydrofuran.
- an electrolytic solution containing a supporting salt and / or an organic solvent used for manufacturing a lithium ion battery can be used.
- a supporting salt a normal salt used in the production of a lithium ion battery can be used, and as the organic solvent, those used in a normal electrolytic solution can be used.
- the electrolyte contained in the electrode or the electrolyte layer is gelled by a gelling agent.
- a supporting salt and an organic solvent may be used individually by 1 type, and may use 2 or more types together.
- the slurry is preferably prepared by dispersing and slurrying the coating active material and, if necessary, the conductive additive at a concentration of 5 to 60% by weight based on the weight of the solvent or the electrolyte.
- the slurry containing the coating active material can be applied to the first main surface or the second main surface of the structure using an arbitrary coating apparatus such as a bar coater or a brush.
- FIG. 8A schematically shows a state in which the slurry is applied on the second main surface of the nonwoven fabric as the structure, and the second main surface 62 of the nonwoven fabric 60 is coated with the coating material 151.
- a slurry containing the positive electrode active material 14 is applied.
- pressurization or decompression is performed to fill the voids in the structure with the coated active material.
- a method of pressurizing operation a method of pressing using a press machine from the slurry application surface can be mentioned.
- a method for the decompression operation a method in which a filter paper or a mesh is applied to the surface on which the slurry is not applied to the structure, and suction is performed by a vacuum pump.
- the structure has voids, it is possible to fill the voids in the structure with the coated active material by pressurization or decompression.
- FIG. 8A shows an arrow indicating the direction in which pressure is applied from above the slurry application surface, and an arrow indicating the direction in which pressure is reduced from below the filter paper 70.
- FIG. 8B shows a positive electrode active material layer 100 in which a coating active material is filled in voids in the structure.
- the positive electrode active material layer 100 illustrated in FIG. 8B is the same as the positive electrode active material layer 100 illustrated in FIG.
- the slurry containing the coating active material is a solvent slurry containing a solvent
- the slurry containing the coating active material is an electrolyte solution slurry containing an electrolytic solution
- the voids in the structure are filled with the coating active material and the electrolytic solution, and the preferred configuration as an electrode for a lithium ion battery Become.
- the electrolyte contained in the electrode or the electrolyte layer is gelled by a gelling agent.
- the coated active material is filled in the voids in the structure by the above process.
- an active material layer can be manufactured.
- Another embodiment of the present invention includes a step of applying a slurry containing a conductive member and a coated active material on a film, and a step of fixing the coated active material and the conductive member on the film by applying pressure or reduced pressure. Including.
- the manufacturing method according to the above aspect is suitable for manufacturing the positive electrode active material layer according to the aspect described with reference to FIG.
- FIG. 9A and FIG. 9B are process diagrams schematically showing a process of fixing the coated active material and the conductive member on the film.
- a slurry containing a coating active material which is a positive electrode active material 14 coated with a conductive material 213 and a coating 151 containing a coating resin and a conductive auxiliary agent 16, is applied onto the film 470.
- Examples of the slurry include those obtained by further adding conductive fibers as a conductive member to the above-described slurry and dispersing the conductive fibers in the slurry.
- the above-described conductive fiber can be used, but the shape of the conductive fiber is preferably such that each of the fibers is an independent shape, such as a nonwoven fabric, a woven fabric, or a knitted fabric. It preferably has no structure. When each of the conductive fibers is independent, the conductive fibers are dispersed in the slurry.
- the slurry may be an electrolyte slurry containing an electrolyte.
- the electrolyte the same electrolyte as that in the above-described electrolyte slurry can be used.
- the slurry is preferably a solvent slurry containing a solvent.
- the electrolyte contained in the electrode or the electrolyte layer is gelled by a gelling agent.
- the film 470 is preferably a film that can separate the coating active material and the conductive member from the electrolytic solution and the solvent in the subsequent pressurization or decompression step.
- the film is made of a highly conductive material (conductive material) because the film can be used as a current collector, and even if the current collector is in contact with the film, the conductivity is not inhibited.
- a material having an electric conductivity of 100 S / cm or more can be suitably used. Examples of materials having such characteristics include filter papers, metal meshes and the like in which conductive fibers such as carbon fibers are blended. Such a material can be used as a current collector.
- the metal mesh it is preferable to use a stainless steel mesh, for example, a SUS316 twilled woven wire mesh (manufactured by Sunnet Kogyo) and the like.
- the mesh opening of the metal mesh is preferably set so that the coated active material and the conductive member do not pass through. For example, it is preferable to use a mesh of 2300 mesh.
- the slurry can be applied onto the film using an arbitrary coating apparatus such as a bar coater or a brush.
- FIG. 9A schematically shows a state in which the slurry is applied on the membrane, and the slurry containing the coated active material and the conductive fibers 213 is applied on the filter paper 470 as the membrane. .
- the coated active material and the conductive member are fixed on the film by applying pressure or reduced pressure.
- the same method as the above-described step can be used, and an electrolytic solution or a solvent is removed from the slurry by pressurization or pressure reduction, and a conductive fiber as a conductive member is coated.
- the active material is fixed on the film, and its shape is maintained so as not to flow.
- FIG. 9B shows a positive electrode active material layer 110 in which conductive fibers 213 as conductive members and a coated active material are fixed on a filter paper 470.
- the film when the film is made of a conductive material, the film can be used as a current collector, and can function as a single current collector by contacting the film with another current collector. You can also. That is, in the positive electrode active material layer 110, the second main surface 121 can be defined as a portion where the conductive fiber 213 as a conductive member is in contact with the filter paper 470.
- the membrane may be a separator.
- the film made of a material having no conductivity include an aramid separator (manufactured by Japan Vilene Co., Ltd.).
- the membrane when the slurry is an electrolyte slurry containing an electrolyte solution, the membrane is a membrane that does not transmit the coating active material but allows the electrolyte solution to pass therethrough. It is preferable to pass through and remove.
- the pressing step is a step of improving the density of the coated active material by increasing the pressure difference further than the pressurization or depressurization in the previous step.
- Such a pressing process is a concept including both an aspect in which pressurization is applied when the previous process is depressurization and an aspect in which the pressurization pressure is further increased when the previous process is pressurization.
- the pressure in the pressing step at this time can be set as appropriate, but is preferably about 1 to 5 kg / cm 2 , for example.
- a step of transferring the coated active material fixed on the film to the main surface of the current collector or the separator is performed, and the first main surface of the active material layer is disposed on the main surface of the separator, or the active material
- the second main surface of the layer forms an electrode disposed on the main surface of the current collector.
- the transferring step it is preferable to transfer the main surface opposite to the film in contact with the main surface of the current collector or separator.
- the film When the film is made of a conductive material and the film is used as a current collector, it is preferable to transfer the main surface opposite to the film in contact with the main surface of the separator. In the case where the film is not used as a current collector, it is preferable to perform a step of peeling the film after the transfer.
- the membrane may be used as part of the separator.
- FIG. 10A and FIG. 10B are process diagrams schematically showing a process of fixing the coated active material and the conductive member with a resin.
- an active material composition including a conductive member, a coated active material, and a resin is prepared.
- conductive member it is preferable to use conductive fibers each having an independent shape, as in the embodiment described with reference to FIGS. 9 (a) and 9 (b).
- the resin it is preferable to use vinyl resin, urethane resin, polyester resin, polyamide resin or the like. These resins are preferable in terms of moldability.
- the resin may be present in the form of a resin solution dissolved in a solvent, or may be present in a solid form such as pellets that are fluidized by heating.
- the resin may be a coating resin contained in the coating agent.
- the conductive member and the active material are preferably dispersed in the resin solution. Further, even when the resin is present in a solid form, it is preferable that the resin, the conductive member, and the active material are dispersed without being unevenly distributed in a specific portion.
- the conductive member and the active material are fixed with resin by heat-pressing the prepared composition for active material.
- the method of the hot press is not particularly limited, but as shown in FIG. 10A, a composition for active material containing a coated active material, conductive fibers 213, and a resin 214 on a plate 570 such as a metal plate.
- coating and heat-pressing from an upper surface is mentioned.
- Application of the active material composition can be performed using an arbitrary coating apparatus such as a bar coater or a brush. Moreover, a heat press can be performed using a normal heat press apparatus.
- the resin is a coating resin for the coating active material
- the conductive member and the coating active material are applied to the plate and heated and pressed, the conductive member and the (coating) active material are formed by the coating resin melted by heating. Fixed.
- the active material fixed by the coating resin is a coated active material that is still coated with the coating resin, but may be peeled off to some extent.
- the conditions of the heating press may be determined as appropriate depending on the curing conditions of the resin used, and are not particularly limited.
- the conditions are 100 to 200 ° C., 0.01 to 5 MPa, and 5 to 300 seconds. It is preferable to heat press under conditions.
- vinyl resin it is preferable to heat press under conditions of 80 to 180 ° C., 0.01 to 5 MPa, and 5 to 300 seconds.
- the positive electrode active material layer 110 in which the conductive fibers 213 and the coating active material are fixed with a resin 214 can be manufactured by heating press.
- the positive electrode active material 14 examples include composite oxides of lithium and transition metals (for example, LiCoO 2 , LiNiO 2 , LiMnO 2 and LiMn 2 O 4 ), transition metal oxides (for example, MnO 2 and V 2 O 5 ), and transition metals. And sulfides (eg, MoS 2 and TiS 2 ) and conductive polymers (eg, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole).
- sulfides eg, MoS 2 and TiS 2
- conductive polymers eg, polyaniline, polyvinylidene fluoride, polypyrrole, polythiophene, polyacetylene, poly-p-phenylene, and polycarbazole.
- Examples of the negative electrode active material 24 include graphite, amorphous carbon, polymer compound fired bodies (for example, those obtained by firing and carbonizing phenol resin and furan resin, etc.), cokes (for example, pitch coke, needle coke, and petroleum coke), Carbon fibers, conductive polymers (such as polyacetylene and polypyrrole), tin, silicon, and metal alloys (such as lithium-tin alloy, lithium-silicon alloy, lithium-aluminum alloy, and lithium-aluminum-manganese alloy) It is done.
- At least one of the positive electrode active material layer and the negative electrode active material layer includes the conductive member and the active material made of the electron conductive material. In that form, at least a part of the surface of the active material is coated with a coating 151 containing a coating resin and a conductive additive 16.
- the conductive auxiliary agent 16 is selected from conductive materials.
- metals ⁇ aluminum, stainless steel (SUS), silver, gold, copper, titanium, etc. ⁇ , carbon ⁇ graphite and carbon black [acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.], etc. ⁇ , And mixtures thereof, but are not limited thereto.
- These conductive assistants may be used alone or in combination of two or more. Moreover, these alloys or metal oxides may be used. From the viewpoint of electrical stability, aluminum, stainless steel, carbon, silver, gold, copper, titanium and mixtures thereof are preferred, silver, gold, aluminum, stainless steel and carbon are more preferred, and carbon is particularly preferred. is there. These conductive aids may be those obtained by coating a conductive material (a metal among the above-mentioned conductive materials) with plating or the like around a particle ceramic material or a resin material.
- the shape (form) of the conductive auxiliary agent is not limited to the particle form, and may be a form other than the particle form, or may be a form put into practical use as a so-called filler-based conductive resin composition such as a carbon nanotube. Good.
- the average particle size (primary particle size) of the conductive assistant is not particularly limited, but is preferably about 0.01 to 10 ⁇ m from the viewpoint of the electric characteristics of the battery.
- the “particle diameter” means the maximum distance L among the distances between any two points on the contour line of the conductive additive.
- the value of “average particle size” is the average value of the particle size of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The calculated value shall be adopted.
- the active material coating resin (also simply referred to as “coating resin”) has a tensile elongation at break of 10% or more in a saturated liquid absorption state.
- the tensile elongation at break in the saturated liquid absorption state is determined by ASTM D683 (test piece shape) by punching the coating resin into a dumbbell shape, dipping in an electrolytic solution at 50 ° C. for 3 days to bring the coating resin into a saturated liquid absorption state. It can be measured according to Type II).
- the tensile elongation at break is a value obtained by calculating the elongation until the test piece breaks in the tensile test according to the following formula.
- Tensile elongation at break (%) [(length of specimen at break ⁇ length of specimen before test) / length of specimen before test] ⁇ 100
- the tensile elongation at break is more preferably 20% or more, and further preferably 30% or more.
- a preferable upper limit of the tensile elongation at break 400% is preferable, and a more preferable upper limit is 300%.
- a urethane resin obtained by reacting an active hydrogen component and an isocyanate component is also preferable as a coating resin. Since the urethane resin has flexibility, coating the lithium ion battery active material with the urethane resin can alleviate the volume change of the electrode and suppress the expansion of the electrode.
- the coating resin has a liquid absorption rate of 10% or more when immersed in an electrolytic solution, and a tensile elongation at break in a saturated liquid absorption state of 10% or more. .
- the liquid absorption rate when immersed in the electrolytic solution is obtained by the following equation by measuring the weight of the coating resin before and after being immersed in the electrolytic solution.
- Absorption rate (%) [(weight of coating resin after immersion in electrolytic solution ⁇ weight of coating resin before immersion in electrolytic solution) / weight of coating resin before immersion in electrolytic solution] ⁇ 100
- An electrolytic solution dissolved to a concentration is used.
- the saturated liquid absorption state refers to a state in which the weight of the coating resin does not increase even when immersed in the electrolyte.
- the coating resin When the liquid absorption is 10% or more, the coating resin sufficiently absorbs the electrolytic solution, and lithium ions can easily permeate the coating resin. The movement of lithium ions is not hindered.
- the liquid absorption rate is preferably 20% or more, and more preferably 30% or more. Moreover, as a preferable upper limit of a liquid absorption rate, it is 400%, and as a more preferable upper limit, it is 300%.
- the lithium ion conductivity of the active material coating resin according to the embodiment of the present invention can be obtained by measuring the conductivity at room temperature of the coating resin after the saturated liquid absorption state is obtained by an AC impedance method.
- the lithium ion conductivity measured by the above method is preferably 1.0 to 10.0 mS / cm, and the performance as a lithium ion battery is sufficiently exhibited within the above range.
- the coating resin has a liquid absorption rate of 10% or more when immersed in an electrolytic solution, a tensile elongation at break in a saturated liquid absorption state of 10% or more, and active hydrogen.
- a urethane resin obtained by reacting a component with an isocyanate component is preferred.
- the active hydrogen component preferably contains at least one selected from the group consisting of polyether diol, polycarbonate diol and polyester diol.
- Polyether diols include polyoxyethylene glycol (hereinafter abbreviated as PEG), polyoxyethyleneoxypropylene block copolymer diol, polyoxyethyleneoxytetramethylene block copolymer diol; ethylene glycol, propylene glycol, 1,4-butanediol 1,6-hexamethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane, 4,4′-bis (2-hydroxyethoxy) -diphenylpropane and other low molecular glycol ethylene oxide adducts; number average molecular weight 2, PEG of 000 or less and dicarboxylic acid [aliphatic dicarboxylic acid having 4 to 10 carbon atoms (for example, succinic acid, adipic acid, sebacic acid, etc.), aromatic dicarboxylic acid having 8 to 15 carbon atoms (for example, terephthalic acid, 1 or more fused polyethers obtained by reacting an ester dio
- the content of the oxyethylene unit is preferably 20% by weight, more preferably 30% by weight or more, and further preferably 40% by weight or more.
- polyoxypropylene glycol polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxypropyleneoxytetramethylene block copolymer diol, and the like.
- PTMG polyoxytetramethylene glycol
- PEG polyoxyethyleneoxypropylene block copolymer diol
- polyoxyethyleneoxytetramethylene block copolymer diol are preferable, and PEG is particularly preferable.
- only 1 type of polyether diol may be used, and 2 or more types of these mixtures may be used.
- Examples of the polycarbonate diol include polyhexamethylene carbonate diol.
- Examples of the polyester diol include a condensed polyester diol obtained by reacting a low-molecular diol and / or a polyether diol having a number average molecular weight of 1,000 or less with one or more of the aforementioned dicarboxylic acids, or a lactone having 4 to 12 carbon atoms. And polylactone diols obtained by ring-opening polymerization.
- Examples of the low molecular diol include the low molecular glycols exemplified in the section of the polyether diol.
- polyether diol having a number average molecular weight of 1,000 or less examples include polyoxypropylene glycol and PTMG.
- lactone examples include ⁇ -caprolactone and ⁇ -valerolactone.
- polyester diol examples include polyethylene adipate diol, polybutylene adipate diol, polyneopentylene adipate diol, poly (3-methyl-1,5-pentylene adipate) diol, polyhexamethylene adipate diol, polycaprolactone diol. And a mixture of two or more of these.
- the active hydrogen component may be a mixture of two or more of the above polyether diol, polycarbonate diol and polyester diol.
- the active hydrogen component is preferably a high molecular diol having a number average molecular weight of 2,500 to 15,000 as an essential component.
- the polymer diol include the polyether diol, polycarbonate diol, and polyester diol described above.
- a polymer diol having a number average molecular weight of 2,500 to 15,000 is preferable because the hardness of the urethane resin is moderately soft and the strength of the film formed on the active material is increased.
- the number average molecular weight of the polymer diol is more preferably 3,000 to 12,500, and further preferably 4,000 to 10,000.
- the number average molecular weight of the polymer diol can be calculated from the hydroxyl value of the polymer diol. The hydroxyl value can be measured according to the description of JIS K1557-1.
- a polymer diol having an active hydrogen component having a number average molecular weight of 2,500 to 15,000 is an essential component, and the solubility parameter (hereinafter abbreviated as SP value) of the polymer diol is 8.0 to 12.0 ( cal / cm 3 ) 1/2 .
- the SP value of the high molecular diol is more preferably 8.5 to 11.5 (cal / cm 3 ) 1/2 , and 9.0 to 11.0 (cal / cm 3 ) 1/2. Further preferred.
- SP value is calculated by Fedors method.
- the SP value can be expressed by the following equation.
- ⁇ 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 SP value of the polymer diol is preferably 8.0 to 12.0 (cal / cm 3 ) 1/2 from the viewpoint of liquid absorption of the urethane resin electrolyte.
- the active hydrogen component is essentially a high molecular diol having a number average molecular weight of 2,500 to 15,000, and the content of the high molecular diol is 20 to 80% by weight based on the weight of the urethane resin. preferable.
- the content of the polymer diol is more preferably 30 to 70% by weight, and further preferably 40 to 65% by weight.
- the content of the polymer diol is 20 to 80% by weight, it is preferable from the viewpoint of liquid absorption of the urethane resin electrolyte.
- the active hydrogen component includes a polymer diol having a number average molecular weight of 2,500 to 15,000 and a chain extender as essential components.
- chain extender examples include low molecular diols having 2 to 10 carbon atoms [for example, ethylene glycol (hereinafter abbreviated as EG), propylene glycol, 1,4-butanediol (hereinafter abbreviated as 14BG), diethylene glycol (hereinafter abbreviated as DEG).
- EG ethylene glycol
- 14BG 1,4-butanediol
- DEG diethylene glycol
- diamines [aliphatic diamines having 2 to 6 carbon atoms (eg, ethylene diamine, 1,2-propylene diamine, etc.), alicyclic diamines having 6 to 15 carbon atoms (eg, isophorone diamine, etc.) , 4,4′-diaminodicyclohexylmethane, etc.], aromatic diamines having 6 to 15 carbon atoms (eg, 4,4′-diaminodiphenylmethane, etc.); monoalkanolamines (eg, monoethanolamine); hydrazine or derivatives thereof (Eg adipic acid dihydrazide) And mixtures of two or more thereof.
- low molecular diols are preferable, and EG, DEG and 14BG are particularly preferable.
- the combination of the polymer diol and the chain extender is preferably a combination of PEG as the polymer diol and EG as the chain extender, or a combination of polycarbonate diol as the polymer diol and EG as the chain extender.
- the active hydrogen component includes a polymer diol (a11) having a number average molecular weight of 2,500 to 15,000, a diol (a12) other than the polymer diol and a chain extender (a13), and (a11) and (a12 ) And the equivalent ratio ⁇ (a11) / (a12) ⁇ of 10/1 to 30/1, and the equivalent ratio of (a11) to the total equivalent of (a12) and (a13) ⁇ (a11) / [( a12) + (a13)] ⁇ is preferably 0.9 / 1 to 1.1 / 1.
- the equivalent ratio ⁇ (a11) / (a12) ⁇ between (a11) and (a12) is more preferably 13/1 to 25/1, and still more preferably 15/1 to 20/1.
- the diol other than the polymer diol is not particularly limited as long as it is a diol and is not included in the above-described polymer diol, and specifically, a diol having a number average molecular weight of less than 2,500, And the diol whose number average molecular weight exceeds 15,000 is mentioned.
- diol examples include the polyether diol, polycarbonate diol, and polyester diol described above.
- the diol other than the polymer diol and the low molecular diol having 2 to 10 carbon atoms contained in the chain extender is not included in the diol other than the polymer diol.
- isocyanate component those conventionally used for polyurethane production can be used.
- isocyanates include aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, Examples thereof include araliphatic diisocyanates having 8 to 15 carbon atoms, modified products of these diisocyanates (carbodiimide-modified products, urethane-modified products, uretdione-modified products, etc.) and mixtures of two or more thereof.
- aromatic diisocyanate examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate, 2,4′- and / or 4,4.
- '-Diphenylmethane diisocyanate hereinafter abbreviated as diphenylmethane diisocyanate
- 4,4'-diisocyanatobiphenyl 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4 4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like.
- aliphatic diisocyanate examples include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, Examples thereof include bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.
- alicyclic diisocyanate examples include isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl) -4-cyclohexylene-1,2. -Dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate and the like.
- araliphatic diisocyanate examples include m- and / or p-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate, and the like.
- aromatic diisocyanates and alicyclic diisocyanates, more preferred are aromatic diisocyanates, and particularly preferred is MDI.
- the equivalent ratio of (a2) / (a11) is preferably 10 to 30/1, more preferably 11 to 28/1.
- the ratio of the isocyanate component exceeds 30 equivalents, a hard coating film is obtained.
- the equivalent ratio of (a2) / [(a11) + (a13)] is usually 0.9 to 1.1 / 1, preferably 0.95 to 1.05 / 1. If it is outside this range, the urethane resin may not have a sufficiently high molecular weight.
- the number average molecular weight of the urethane resin is preferably 40,000 to 500,000, more preferably 50,000 to 400,000.
- the strength of the coating is low, and when it exceeds 500,000, the solution viscosity increases and a uniform coating may not be obtained.
- the number average molecular weight of the urethane resin is measured by gel permeation chromatography (hereinafter abbreviated as GPC) using DMF as a solvent and polyoxypropylene glycol as a standard substance.
- GPC gel permeation chromatography
- the sample concentration may be 0.25% by weight
- the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.
- Urethane resin can be produced by reacting an active hydrogen component and an isocyanate component.
- a polymer diol and a chain extender are used as active hydrogen components, and a one-shot method in which an isocyanate component, a polymer diol and a chain extender are reacted simultaneously, or after a polymer diol and an isocyanate component are reacted first
- a prepolymer method in which a chain extender is continuously reacted.
- the urethane resin can be produced in the presence or absence of a solvent inert to the isocyanate group.
- Suitable solvents in the presence of a solvent include amide solvents [dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide, etc.], sulfoxide solvents (dimethylsulfoxide, etc.), ketone solvents [methyl ethyl ketone, methyl isobutyl ketone.
- Etc. aromatic solvents (toluene, xylene, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (ethyl acetate, butyl acetate, etc.) and mixtures of two or more thereof.
- aromatic solvents toluene, xylene, etc.
- ether solvents dioxane, tetrahydrofuran, etc.
- ester solvents ethyl acetate, butyl acetate, etc.
- amide solvents, ketone solvents, aromatic solvents, and mixtures of two or more thereof are preferred.
- the reaction temperature may be the same as that usually used for the urethanization reaction, and is usually 20 to 100 ° C. when a solvent is used, and usually 20 to 220 ° C. when no solvent is used.
- a catalyst usually used in a polyurethane reaction for example, amine-based catalyst (triethylamine, triethylenediamine, etc.), tin-based catalyst (dibutyltin dilaurate, etc.)] can be used.
- a polymerization terminator for example, monohydric alcohol (ethanol, isopropyl alcohol, butanol, etc.), monovalent amine (dimethylamine, dibutylamine, etc.), etc.
- monohydric alcohol ethanol, isopropyl alcohol, butanol, etc.
- monovalent amine dimethylamine, dibutylamine, etc.
- Urethane resin can be produced by a production apparatus usually employed in the industry. When no solvent is used, a manufacturing apparatus such as a kneader or an extruder can be used.
- the urethane resin produced in this way has a solution viscosity of usually 10 to 10,000 poise / 20 ° C. measured as a 30% by weight (solid content) DMF solution, and practically preferred is 100 to 2,000 poise. / 20 ° C.
- a polymer having a vinyl monomer as an essential constituent monomer is also preferable as the coating resin. Since a polymer having a vinyl monomer as an essential constituent monomer has flexibility, coating the active material with the polymer can alleviate the volume change of the electrode and suppress the expansion of the electrode.
- the coating resin has a liquid absorption rate of 10% or more when immersed in an electrolytic solution, a tensile elongation at break in a saturated liquid absorption state of 10% or more, and a vinyl monomer as an essential constituent monomer. It is preferable to comprise the polymer to do.
- a vinyl monomer having a carboxyl group as a vinyl monomer and a vinyl monomer represented by the following general formula (1).
- R 1 is a hydrogen atom or a methyl group
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 4 to 36 carbon atoms.
- vinyl monomers having a carboxyl group examples include monocarboxylic acids having 3 to 15 carbon atoms such as (meth) acrylic acid, crotonic acid, cinnamic acid; (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, citraconic acid, Examples thereof include dicarboxylic acids having 4 to 24 carbon atoms such as mesaconic acid; polycarboxylic acids having 6 to 24 carbon atoms such as aconitic acid and trivalent to tetravalent or higher valences.
- (meth) acrylic acid is preferable, and methacrylic acid is particularly preferable.
- R 1 represents a hydrogen atom or a methyl group.
- R 1 is preferably a methyl group.
- R 2 is a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 4 to 36 carbon atoms. Specific examples of R 2 include a methyl group, an ethyl group, a propyl group, and a 1-alkylalkyl group.
- a methyl group, an ethyl group, and a 2-alkylalkyl group are preferable from the viewpoint of absorbing the electrolyte solution, and a 2-ethylhexyl group and a 2-decyltetradecyl group are more preferable.
- the monomer constituting the polymer includes a copolymerizable vinyl monomer (b3) that does not contain active hydrogen. Also good.
- Examples of the copolymerizable vinyl monomer (b3) containing no active hydrogen include the following (b31) to (b35).
- the monool includes (i) aliphatic monool [methanol, ethanol, n- and i-propyl.
- Alcohol n-butyl alcohol, n-pentyl alcohol, n-octyl alcohol, nonyl alcohol, decyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.], (ii) alicyclic monool [ Cyclohexyl alcohol etc.], (iii) araliphatic monools [benzyl alcohol etc.] and mixtures of two or more thereof.
- (B32) Poly (n 2 to 30) oxyalkylene (carbon number 2 to 4) alkyl (carbon number 1 to 18) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meth) Acrylate, propylene oxide of methanol (hereinafter abbreviated as PO), 10 mol adduct (meth) acrylate, etc.]
- Nitrogen-containing vinyl compound (b33-1) Amido group-containing vinyl compound (i) (Meth) acrylamide compound having 3 to 30 carbon atoms, such as N, N-dialkyl (1 to 6 carbon atoms) or diaralkyl (carbon number) 7-15) (Meth) acrylamide [N, N-dimethylacrylamide, N, N-dibenzylacrylamide, etc.], diacetone acrylamide (ii) Contains an amide group having 4 to 20 carbon atoms excluding the above (meth) acrylamide compound
- acetoxystyrene (B35-2) Vinyl ether Aliphatic vinyl ether [carbon number 3 to 15, for example, vinyl alkyl (carbon number 1 to 10) ether [vinyl methyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, etc.], vinyl alkoxy (carbon number 1 to 6) alkyl (1 to 4 carbon atoms) ether [vinyl-2-methoxyethyl ether, methoxybutadiene, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2 -Ethyl mercaptoethyl ether, etc.], poly (2-4) (meth) allyloxyalkanes (2-6 carbon atoms) [diallyloxyethane, triaryloxyethane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] ] Aromatic vinyl ether (C8
- the content of the vinyl monomer (b1) having a carboxyl group, the vinyl monomer (b2) represented by the general formula (1) and the copolymerizable vinyl monomer (b3) not containing active hydrogen is (B1) is preferably 0.1 to 80% by weight, (b2) is preferably 0.1 to 99.9% by weight, and (b3) is preferably 0 to 99.8% by weight.
- the liquid absorbency to the electrolyte is good.
- More preferable contents are 30 to 60% by weight of (b1), 5 to 60% by weight of (b2), and 5 to 80% by weight of (b3). Further more preferable contents are 35 to 60% of (b1). 50% by weight, (b2) is 15 to 45% by weight, and (b3) is 20 to 60% by weight.
- the preferable lower limit of the number average molecular weight of the polymer is 3,000, more preferably 50,000, particularly preferably 100,000, most preferably 200,000, and the preferable upper limit is 2,000,000, more preferably 1. 500,000, particularly preferably 1,000,000, most preferably 800,000.
- the number average molecular weight of the polymer can be determined by GPC (gel permeation chromatography) measurement under the following conditions.
- the solubility parameter (SP value) of the polymer is preferably 9.0 to 20.0 (cal / cm 3 ) 1/2 .
- the SP value of the polymer is more preferably 10.0 to 18.0 (cal / cm 3 ) 1/2 , and further preferably 11.5 to 14.0 (cal / cm 3 ) 1/2. preferable.
- the SP value of the polymer is preferably 9.0 to 20.0 (cal / cm 3 ) 1/2 in view of the absorption of the electrolytic solution.
- the glass transition point of the polymer is preferably 80 to 200 ° C., more preferably 90 to 180 ° C. from the viewpoint of heat resistance of the battery. Particularly preferred is 100 to 150 ° C.
- the polymer can be produced by a known polymerization method (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
- azo initiators [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile, etc.), peroxide initiators] Agents (benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.)] and the like].
- the amount of the polymerization initiator used is preferably 0.01 to 5% by weight, more preferably 0.03 to 2% by weight, based on the total weight of the monomers.
- Examples of the solvent used in the solution polymerization include esters (having 2 to 8 carbon atoms such as ethyl acetate and butyl acetate), alcohols (having 1 to 8 carbon atoms such as methanol, ethanol and octanol), hydrocarbons (having carbon atoms).
- the monomer concentration is usually 5 to 900%, preferably 10 to 400%, and the monomer concentration is usually 10 to 95% by weight, preferably 20 to 90% by weight.
- Examples of the dispersion medium in emulsion polymerization and suspension polymerization include water, alcohol (for example, ethanol), ester (for example, ethyl propionate), light naphtha, and the like.
- As the emulsifier higher fatty acid (10 to 24 carbon atoms) metal salt.
- higher alcohol (10 to 24 carbon atoms) sulfate metal salt for example, sodium lauryl sulfate
- sulfoethyl sodium methacrylate dimethylaminomethyl methacrylate, etc.
- the monomer concentration of the solution or dispersion is usually 5 to 95% by weight, and the amount of the polymerization initiator used is usually 0.01 to 5% based on the total weight of the monomer, preferably from the viewpoint of adhesive strength and cohesive strength. 05-2%.
- chain transfer agents such as mercapto compounds (such as dodecyl mercaptan and n-butyl mercaptan) and halogenated hydrocarbons (such as carbon tetrachloride, carbon tetrabromide and benzyl chloride) can be used.
- the amount used is usually 2% or less based on the total weight of the monomer, and preferably 0.5% or less from the viewpoint of adhesive strength and cohesive strength.
- the system temperature in the polymerization reaction is usually ⁇ 5 to 150 ° C., preferably 30 to 120 ° C.
- the reaction time is usually 0.1 to 50 hours, preferably 2 to 24 hours
- the end point of the reaction is unreacted It can be confirmed that the amount of monomer is usually 5% by weight or less, preferably 1% by weight or less of the total amount of monomers used.
- the coating resin may be a crosslinked polymer obtained by crosslinking a polymer with a polyepoxy compound and / or a polyol compound.
- cross-linked polymer it is preferable to cross-link the polymer using a cross-linking agent having a reactive functional group that reacts with active hydrogen such as a carboxyl group in the polymer, and a polyepoxy compound and / or a polyol compound is used as the cross-linking agent. It is more preferable to use
- Polyepoxy compounds having an epoxy equivalent of 80 to 2,500 such as glycidyl ether [bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, pyrogallol triglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neodymium Pentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, polyethylene glycol (Mw 200-2,000) diglycidyl ether, polypropylene glycol (Mw 200-2,000) diglycidyl ether, alkylene oxide 1 of bisphenol A ⁇ 20 mol adduct diglycidyl ether, etc.]; glycidyl ester (diglyceryl phthalate) Glycidylamine (N, N-diglycidylaniline, N, N-diglycidy
- polyol compounds include low molecular weight polyhydric alcohols [aliphatic and alicyclic diols having 2 to 20 carbon atoms [EG, DEG, propylene glycol, 1,3-butylene glycol, 1,4BG, 1,6-hexanediol.
- the use amount of the cross-linking agent is preferably an equivalent ratio of the active hydrogen-containing group in the polymer and the reactive functional group in the cross-linking agent from the viewpoint of absorbing the electrolyte solution, preferably 1: 0.01 to 2, The amount is preferably 1: 0.02 to 1.
- Examples of a method for crosslinking a polymer using a crosslinking agent include a method in which an active material is coated with a coating resin made of a polymer and then crosslinked. Specifically, a resin solution containing an active material and a polymer is mixed and removed to produce a coated active material in which the active material is coated with a resin, and then a solution containing a crosslinking agent is mixed into the coated active material. And heating to cause a solvent removal and a crosslinking reaction to coat the active material with a crosslinked polymer.
- the heating temperature is preferably 70 ° C. or higher when a polyepoxy compound is used as a crosslinking agent, and preferably 120 ° C. or higher when a polyol compound is used.
- the coated active material coated with the coating agent is, for example, a resin solution containing a coating resin (coating resin solution) for 1 to 90 minutes in a state where the active material is put in a universal mixer and stirred at 10 to 500 rpm.
- the mixture is added dropwise, mixed with a conductive additive, heated to 50 to 200 ° C. with stirring, depressurized to 0.007 to 0.04 MPa, and held for 10 to 150 minutes.
- a solvent of a resin solution alcohol, such as methanol, ethanol, or isopropanol, can be used conveniently.
- the coating resin solution contains a coating resin and a solvent, but in some cases, the coating resin solution may be produced by mixing a coating resin and a conductive additive.
- the active material can be coated with the coating resin solution (coating agent) by further mixing the coating resin solution mixed in advance with the active material.
- the coating resin solution coating agent
- the coating resin, the active material, and the conductive assistant are mixed at the same time, and the coating resin and the conductive assistant are included on the surface of the active material. You may coat
- the coating resin is mixed with the active material, and further the conductive assistant is mixed, so that the coating resin and the conductive assistant are mixed on the surface of the active material.
- the coated active material at least a part of the surface of the active material is coated with a coating agent containing a coating resin and a conductive auxiliary agent. It can be said that it has a shell structure.
- the average particle size of the core part (active material) is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m from the viewpoint of high output.
- the thickness of the shell portion is not particularly limited, but is preferably 0.01 to 5 ⁇ m, more preferably 0.1 to 2 ⁇ m, as the thickness in the state where no gel is formed.
- the two electrodes having different polarities or the electrolyte contained in the electrolyte layer is a gel electrolyte
- the electrolyte contained in the active material layer in the two electrodes having different polarities is a gel. It can be a state electrolyte.
- the method of including the gel electrolyte in the active material layer is not particularly limited, and in the form of FIG. 8, the second main surface 62 of the nonwoven fabric 60 includes the gel electrolyte in the slurry containing the coated active material. May be.
- a gel electrolyte may be included in the slurry containing the conductive member 213 and the coating active material.
- FIG. 9 a gel electrolyte may be included in the slurry containing the conductive member 213 and the coating active material.
- a gel electrolyte may be included in the composition for active material including the positive electrode active material 14, the conductive fiber 213, and the resin 214. Further, the active material layer produced as described above can be included by impregnating the gel electrolyte and moistening it.
- the gel electrolyte can be produced by having a step including a gelling agent in the liquid electrolyte.
- the liquid electrolyte may have a form in which a supporting salt is dissolved in an organic solvent.
- an organic solvent for example, a lactone compound, a cyclic or chain carbonate ester, a chain carboxylate ester, a cyclic or chain ether, a phosphate ester, a nitrile compound, an amide compound, a sulfone, a sulfolane, or a mixture thereof is used.
- Examples thereof include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
- organic solvents lactone compounds, cyclic carbonates, chain carbonates and phosphates are preferable from the viewpoint of battery output and charge / discharge cycle characteristics, and more preferable are lactone compounds, cyclic carbonates and chain esters.
- Carbonic acid ester is particularly preferable, and a mixed liquid of cyclic carbonate and chain carbonate is preferable. Most preferred is a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC).
- the gel electrolyte obtained by including a gelling agent in the liquid electrolyte preferably has an electric conductivity of 0.1 mS / cm or more, more preferably an electric conductivity of 0.1 to 2 mS / cm. 0.5 to 2 mS / cm.
- the conductivity of the gel material is used as an indicator of the strength of the gel material. It is possible.
- the electrical conductivity of the gel electrolyte used in the nonaqueous electrolyte secondary battery of the present invention can be measured by the following method, and the electrical conductivity can be obtained by adding a preferred part of the gelling agent described below to the liquid electrolyte. Can be made a preferable range.
- a gel electrolyte is produced by gelling a mixture in which a liquid electrolyte and a gelling agent are mixed in the same ratio as that used in the non-aqueous electrolyte secondary battery of the present invention.
- measurement is performed at 25 ° C. by the AC impedance method according to the method of measuring the conductivity of JIS R 1661-2004 fine ceramics ion conductor.
- the gelling agent for example, a gelling monomer can be used.
- the gelling monomer include a monomer having two or more polymerizable groups capable of thermal polymerization in one molecule, or an oligomer.
- the matrix polymer forming the gel electrolyte contains a carboxylic acid ester as a functional group. If the gel matrix polymer of the electrolytic solution is a gel matrix polymer having the same functional group as the functional group of the electrolytic solution constituting solvent, a carboxylic acid ester is included as a functional group.
- Examples of the gelling monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene di (meth) acrylate, dipropylene di ( 2) such as (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate
- Functional acrylates trifunctional acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, although such tetrafunctional acrylates such as pentaerythritol tetra
- monomers such as urethane acrylate and urethane methacrylate, copolymer oligomers thereof, and copolymer oligomers with acrylonitrile are exemplified, but not limited thereto. These gelling monomers are preferably used in combination of two or more.
- the amount of the gelling monomer used (the total amount when two or more are used in combination) is not particularly limited.
- a liquid electrolyte organic Solvent
- the cycle characteristics are further improved.
- the matrix polymer forming the gel electrolyte contains a thermal polymerization initiator in an electrolytic solution containing a mixture of at least a molecule having two polymerizable groups and a molecule having three polymerizable groups. Not obtained by having thermal polymerization to gel the electrolyte.
- a thermal polymerization initiator in an electrolytic solution containing a mixture of at least a molecule having two polymerizable groups and a molecule having three polymerizable groups.
- 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 type of thermal polymerization initiator is not particularly limited, but is preferably one that can react at a temperature at which the electrolytic solution does not decompose and the decomposition product is not easily oxidized / reduced, such as t-butyl peroxypivalate, t-butyl.
- Peroxyneodecanoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, etc. can be used .
- the time for thermal polymerization is not particularly limited, but is about 10 to 300 minutes.
- At least one of the active material layers includes a conductive member made of an electron conductive material and a coated active material.
- the electrolytic solution may contain an ion conductive polymer, a supporting salt, and the like.
- Non conductive polymer examples include polyethylene oxide (PEO) -based and polypropylene oxide (PPO) -based polymers.
- LiPF 6 LiBF 4, LiSbF 6, LiAsF 6 and LiClO 4 lithium salts of inorganic acids such as, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2 and LiC Examples thereof include lithium salts of organic acids such as (CF 3 SO 2 ) 3 .
- LiPF 6 is preferable from the viewpoint of battery output and charge / discharge cycle characteristics.
- the compounding ratio of the components contained in the active material layer is not particularly limited.
- the blending ratio can be adjusted by appropriately referring to known knowledge about lithium ion secondary batteries.
- the thickness of each active material layer is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to.
- the electrolyte used for the electrolyte layer 17 of this embodiment may be a gel electrolyte. Since the explanation of the gel electrolyte has been described above, it is omitted here.
- 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.
- 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), the thickness may be 4 to 60 ⁇ m in a single layer or multiple layers. preferable.
- the fine pore diameter of the microporous (microporous membrane) separator is preferably 1 ⁇ m or less (usually a pore diameter of about several tens of nm). In this example, a microporous separator was used.
- the 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 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 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.
- ⁇ Positive electrode lead and negative electrode lead> ⁇ Positive electrode lead and negative electrode lead> Moreover, although illustration is abbreviate
- materials used in known lithium ion secondary batteries can be similarly employed.
- heat-shrinkable heat-shrinkable parts are removed from the exterior so that they do not affect products (for example, automobile parts, especially electronic devices) by touching peripheral devices or wiring and causing leakage. It is preferable to coat with a tube or the like.
- 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.
- any material constituting the seal portion any material having insulating properties, sealability against falling off of solid electrolyte, sealability against moisture permeation from the outside (sealing property), heat resistance under battery operating temperature, etc. Good.
- 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 As the battery outer case, a known metal can case can be used, and a bag-like case using a laminate film 29 containing aluminum that can cover the power generation element as shown in FIG. 1 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 preferred 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 sheet-like electrode described above, so that the active material can be expanded and contracted even when an active material having a large battery capacity is used. The stress due to can be relieved, and the 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. 11 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 shown in FIG. 1 described above.
- the power generation element 57 is formed by laminating a positive electrode, an electrolyte layer 17 and a negative electrode. According to a preferred embodiment, a plurality of such layers are stacked.
- 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. 11 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.
- a travel distance (cruising range) by one charge is 100 km.
- 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, the problem of deterioration of battery characteristics (cycle characteristics) due to the collapse of the crystal structure accompanying the 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.
- an active material whose surface is coated with a conductive additive and a gel matrix polymer is used.
- conventional lithium ion secondary batteries use polymer compounds such as starch, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, styrene-butadiene rubber, polyethylene and polypropylene as binders.
- a binder may not be used.
- the battery by gelling the electrolyte of a battery using an electrode containing a conductive member such as carbon fiber, the battery has excellent rate characteristics, and even if it is thick, the electrode does not crack and is not uniform. Even when pressure is applied, the electrode is not partially deformed, so that the cycle durability of the battery can be improved.
- a conductive member such as carbon fiber
- 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, by connecting a plurality of these detachable small assembled batteries in series or in parallel, 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.
- Part means “part by mass” unless otherwise specified.
- an initiator solution prepared by dissolving 0.583 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 26 parts of ethyl acetate was continuously added over 2 hours using a dropping funnel. . Furthermore, the polymerization was continued for 4 hours at the boiling point. After removing the solvent to obtain 582 parts of resin, 1,360 parts of isopropanol was added to obtain a coating resin solution comprising a vinyl resin having a resin concentration of 30% by weight.
- ⁇ Production of coated positive electrode active material 96 parts by weight of LiCoO 2 powder (Cell Seed C-8G manufactured by Nippon Kagaku Kogyo Co., Ltd.) was placed in a universal mixer and stirred at room temperature (25 ° C.) and 150 rpm. %) was added dropwise over 60 minutes so as to be 2 parts by weight as resin solids, and further stirred for 30 minutes.
- LiCoO 2 powder Cell Seed C-8G manufactured by Nippon Kagaku Kogyo Co., Ltd.
- acetylene black [DENKA BLACK (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.] (average particle size (primary particle size): 0.036 ⁇ m) in a stirred state was mixed in three portions, and 30 While stirring for a minute, the temperature was raised to 70 ° C., and the pressure was reduced to 100 mmHg and held for 30 minutes.
- the coated positive electrode active material was obtained by the above operation. The tensile elongation at break in the saturated liquid absorption state was 50%. Assuming that the coated positive electrode active material has a core-shell structure, the average particle diameter of the LiCoO 2 powder as the core was 8 ⁇ m. The thickness of the shell was 0.14 ⁇ m when simply calculated as the total coating.
- LiPF 6 was dissolved at a rate of 1 mol / L in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) (volume ratio 1: 1) to prepare an electrolytic solution for a lithium ion battery.
- EC ethylene carbonate
- DEC diethyl carbonate
- Electrolytic Solution 2 To 100 parts by weight of the electrolytic solution 1, 3.8 parts by weight of triethylene glycol diacrylate and 1 part by weight of trimethylolpropane triacrylate were added and mixed well as a gelling agent. Thereafter, 0.5 parts by weight of t-butyl peroxypivalate was mixed as a polymerization initiator. The mixture obtained by mixing was placed in a thermostat at 80 ° C. and thermally polymerized for 2 hours to prepare conductivity for conductivity measurement, adjusted to 25 ° C., and then JIS R 1661-2004 Fine Ceramics Ion Conduction The conductivity was measured by the AC impedance method according to the method for measuring the electrical conductivity of the body. The conductivity was 0.7 mS / cm.
- Carbon fiber (Donakabo Mild S-243 manufactured by Osaka Gas Chemical Co., Ltd .: average fiber length 500 ⁇ m, average fiber diameter 13 ⁇ m: electrical conductivity 200 mS / cm) was prepared as a conductive member.
- the slurry was prepared by mixing 1.75 parts by weight of the carbon fiber and 98.25 parts by weight of the coated positive electrode active material with 1000 parts by weight of propylene carbonate.
- An aramid nonwoven fabric (20 ⁇ m) was laid on a glass filter of a separable flask whose suction part was a glass filter with a diameter of 70 mm.
- the slurry dispersed in propylene carbonate was poured there, suction filtration (depressurization) and pressurization with a pressurization pressure of 1.5 kg / cm 2 to fix the coated positive electrode active material and the carbon fiber to the non-woven fabric of aramid,
- a positive electrode active material layer was prepared.
- the coating density of the positive electrode active material layer was 120 mg / cm 2 .
- the film thickness of the positive electrode active material layer at this time was 500 ⁇ m.
- the above electrolyte solution 1 was added and the product was laminated (on the negative electrode) with the PP separator interposed therebetween (that is, Al current collector, coated positive electrode active material layer, aramid nonwoven fabric, PP separator, Li metal foil) , Cu current collectors were laminated in order, and aramid was also used as a separator in combination with polypropylene).
- the Al lead was taken out from the positive electrode Al current collector, the Ni lead was taken out from the negative electrode Cu current collector, and housed in an aluminum laminate pack (laminate film) and heat-sealed under reduced pressure.
- the cell was pressed with two SUS plates via a rubber sheet.
- Example 1 A cell was constructed in the same manner as in Reference Example 1 except that the electrolytic solution 1 was changed to the electrolytic solution 2.
- Example 2 A cell was constructed in the same manner as in Reference Example 1 except that the electrolytic solution 1 was changed to the electrolytic solution 3.
- the battery was charged to 4.2V with a CC-CV of 0.2C for a total of 8 hours, and discharged to 2.5V with a CC of 0.2C. Thereafter, the charge / discharge rate is 0.5C, 3 hours, and CC discharge is performed at 0.5C, and the capacity maintenance rate after 50 cycles is a value for the third discharge capacity under the 0.5C charge / discharge condition.
- the active material is coated with a conductive additive and a coating resin (gel matrix polymer), and a slurry is prepared by adding a conductive member (carbon fiber).
- a slurry is prepared by adding a conductive member (carbon fiber).
- a thick film electrode having good reactivity can be formed, and a battery having excellent cycle durability can be obtained by gelling the electrolyte.
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Abstract
Description
図1は、本発明の一実施形態である双極型二次電池を模式的に表した断面図である。図1に示す双極型二次電池10は、実際に充放電反応が進行する略矩形の発電要素21が、電池外装材であるラミネートフィルム29の内部に封止された構造を有する。
集電体は、正極活物質層と接する一方の面から、負極活物質層と接する他方の面へと電子の移動を媒介する機能を有する。集電体を構成する材料に特に制限はないが、例えば、金属や、導電性を有する樹脂が採用されうる。
本発明の実施形態によれば、正極活物質層および負極活物質層のうち少なくとも一方が、電子伝導材料からなる導電部材および活物質を含む。その形態においては、活物質の表面の少なくとも一部は、被覆用樹脂および導電助剤を含む被覆剤によって被覆されている。また、本発明の実施形態によれば、前記活物質層が、前記電解質層側に接触する第1主面と、前記集電体側に接触する第2主面とを有する。そして、前記導電部材の少なくとも一部は、前記第1主面から前記第2主面までを電気的に接続する導電通路を形成している。
正極活物質14としては、リチウムと遷移金属との複合酸化物(例えばLiCoO2、LiNiO2、LiMnO2およびLiMn2O4)、遷移金属酸化物(例えばMnO2およびV2O5)、遷移金属硫化物(例えばMoS2およびTiS2)および導電性高分子(例えばポリアニリン、ポリフッ化ビニリデン、ポリピロール、ポリチオフェン、ポリアセチレン、ポリ-p-フェニレンおよびポリカルバゾール)等が挙げられる。
負極活物質24としては、黒鉛、アモルファス炭素、高分子化合物焼成体(例えばフェノール樹脂およびフラン樹脂等を焼成し炭素化したもの等)、コークス類(例えばピッチコークス、ニードルコークスおよび石油コークス等)、炭素繊維、導電性高分子(例えばポリアセチレンおよびポリピロール等)、スズ、シリコン、および金属合金(例えばリチウム-スズ合金、リチウム-シリコン合金、リチウム-アルミニウム合金およびリチウム-アルミニウム-マンガン合金等)等が挙げられる。
上記のように、本発明の実施形態によれば、正極活物質層および負極活物質層のうち少なくとも一方が、電子伝導材料からなる導電部材および活物質を含む。その形態においては、活物質の表面の少なくとも一部は、被覆用樹脂および導電助剤16を含む被覆剤151によって被覆されている。
導電助剤16としては、導電性を有する材料から選択される。
本発明の好ましい実施形態によれば、活物質被覆用樹脂(単に「被覆用樹脂」ともいう)は、飽和吸液状態での引張破断伸び率は10%以上である。
被覆用樹脂の飽和吸液状態での引張破断伸び率が10%以上であると、被覆用樹脂が適度な柔軟性を有するため、活物質を被覆することにより電極の体積変化を緩和し、電極の膨脹を抑制することができる。引張破断伸び率は20%以上であることがより好ましく、30%以上であることがさらに好ましい。また、引張破断伸び率の好ましい上限値としては、400%であることが好ましく、より好ましい上限値としては300%である。
吸液率を求めるための電解液としては、エチレンカーボネート(EC)、ジエチルカーボネート(DEC)を体積割合でEC:DEC=3:7で混合した混合溶媒に、電解質としてLiPF6を1mol/Lの濃度になるように溶解した電解液を用いる。
但し、式中、ΔHはモル蒸発熱(cal)を、Vはモル体積(cm3)を表す。
式(1)中、R1は水素原子またはメチル基であり、R2は、炭素数1~4の直鎖のアルキル基または炭素数4~36の分岐アルキル基である。
上記モノオールとしては、(i)脂肪族モノオール[メタノール、エタノール、n-およびi-プロピルアルコール、n-ブチルアルコール、n-ペンチルアルコール、n-オクチルアルコール、ノニルアルコール、デシルアルコール、ラウリルアルコール、トリデシルアルコール、ミリスチルアルコール、セチルアルコール、ステアリルアルコール等]、(ii)脂環式モノオール[シクロヘキシルアルコール等]、(iii)芳香脂肪族モノオール[ベンジルアルコール等]およびこれらの2種以上の混合物が挙げられる。
(b33)窒素含有ビニル化合物
(b33-1)アミド基含有ビニル化合物
(i)炭素数3~30の(メタ)アクリルアミド化合物、例えばN,N-ジアルキル(炭素数1~6)もしくはジアラルキル(炭素数7~15)(メタ)アクリルアミド[N,N-ジメチルアクリルアミド、N,N-ジベンジルアクリルアミドなど]、ジアセトンアクリルアミド
(ii)上記(メタ)アクリルアミド化合物を除く、炭素数4~20のアミド基含有ビニル化合物、例えばN-メチル-N-ビニルアセトアミド、環状アミド(ピロリドン化合物(炭素数6~13、例えば、N-ビニルピロリドンなど))
(b33-2)(メタ)アクリレート化合物
(i)ジアルキル(炭素数1~4)アミノアルキル(炭素数1~4)(メタ)アクリレート[N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレート、t-ブチルアミノエチル(メタ)アクリレート、モルホリノエチル(メタ)アクリレートなど]
(ii)4級アンモニウム基含有(メタ)アクリレート〔3級アミノ基含有(メタ)アクリレート[N,N-ジメチルアミノエチル(メタ)アクリレート、N,N-ジエチルアミノエチル(メタ)アクリレートなど]の4級化物(前記の4級化剤を用いて4級化したもの)など〕
(b33-3)複素環含有ビニル化合物
ピリジン化合物(炭素数7~14、例えば2-および4-ビニルピリジン)、イミダゾール化合物(炭素数5~12、例えばN-ビニルイミダゾール)、ピロール化合物(炭素数6~13、例えばN-ビニルピロール)、ピロリドン化合物(炭素数6~13、例えばN-ビニル-2-ピロリドン)
(b33-4)ニトリル基含有ビニル化合物
炭素数3~15のニトリル基含有ビニル化合物、例えば(メタ)アクリロニトリル、シアノスチレン、シアノアルキル(炭素数1~4)アクリレート
(b33-5)その他ビニル化合物
ニトロ基含有ビニル化合物(炭素数8~16、例えばニトロスチレン)など
(b34)ビニル炭化水素
(b34-1)脂肪族ビニル炭化水素
炭素数2~18またはそれ以上のオレフィン[エチレン、プロピレン、ブテン、イソブチレン、ペンテン、ヘプテン、ジイソブチレン、オクテン、ドデセン、オクタデセンなど]、炭素数4~10またはそれ以上のジエン[ブタジエン、イソプレン、1,4-ペンタジエン、1,5-ヘキサジエン、1,7-オクタジエンなど]など
(b34-2)脂環式ビニル炭化水素
炭素数4~18またはそれ以上の環状不飽和化合物、例えばシクロアルケン(例えばシクロヘキセン)、(ジ)シクロアルカジエン[例えば(ジ)シクロペンタジエン]、テルペン(例えばピネン、リモネンおよびインデン)
(b34-3)芳香族ビニル炭化水素
炭素数8~20またはそれ以上の芳香族不飽和化合物、例えばスチレン、α-メチルスチレン、ビニルトルエン、2,4-ジメチルスチレン、エチルスチレン、イソプロピルスチレン、ブチルスチレン、フェニルスチレン、シクロヘキシルスチレン、ベンジルスチレン
(b35)ビニルエステル、ビニルエーテル、ビニルケトン、不飽和ジカルボン酸ジエステル
(b35-1)ビニルエステル
脂肪族ビニルエステル[炭素数4~15、例えば脂肪族カルボン酸(モノ-およびジカルボン酸)のアルケニルエステル(例えば酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ジアリルアジペート、イソプロペニルアセテート、ビニルメトキシアセテート)]、芳香族ビニルエステル[炭素数9~20、例えば芳香族カルボン酸(モノ-およびジカルボン酸)のアルケニルエステル(例えばビニルベンゾエート、ジアリルフタレート、メチル-4-ビニルベンゾエート)、脂肪族カルボン酸の芳香環含有エステル(例えばアセトキシスチレン)]
(b35-2)ビニルエーテル
脂肪族ビニルエーテル〔炭素数3~15、例えばビニルアルキル(炭素数1~10)エーテル[ビニルメチルエーテル、ビニルブチルエーテル、ビニル2-エチルヘキシルエーテルなど]、ビニルアルコキシ(炭素数1~6)アルキル(炭素数1~4)エーテル[ビニル-2-メトキシエチルエーテル、メトキシブタジエン、3,4-ジヒドロ-1,2-ピラン、2-ブトキシ-2’-ビニロキシジエチルエーテル、ビニル-2-エチルメルカプトエチルエーテルなど]、ポリ(2~4)(メタ)アリロキシアルカン(炭素数2~6)[ジアリロキシエタン、トリアリロキシエタン、テトラアリロキシブタン、テトラメタアリロキシエタンなど]〕
芳香族ビニルエーテル(炭素数8~20、例えばビニルフェニルエーテル、フェノキシスチレン)
(b35-3)ビニルケトン
脂肪族ビニルケトン(炭素数4~25、例えばビニルメチルケトン、ビニルエチルケトン)
芳香族ビニルケトン(炭素数9~21、例えばビニルフェニルケトン)
(b35-4)不飽和ジカルボン酸ジエステル
炭素数4~34の不飽和ジカルボン酸ジエステル、例えばジアルキルフマレート(2個のアルキル基は、炭素数1~22の、直鎖、分枝鎖もしくは脂環式の基)、ジアルキルマレエート(2個のアルキル基は、炭素数1~22の、直鎖、分枝鎖もしくは脂環式の基)
上記(b3)として例示したもののうち電解液の吸液および耐電圧の観点から好ましいのは、(b31)、(b32)および(b33)であり、さらに好ましいのは、(b31)のうちのメチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレートである。
溶媒:オルトジクロロベンゼン
標準物質:ポリスチレン
サンプル濃度:3mg/ml
カラム固定相:PLgel 10μm、MIXED-B 2本直列(ポリマーラボラトリーズ社製)
カラム温度:135℃
重合体の溶解度パラメータ(SP値)は9.0~20.0(cal/cm3)1/2であることが好ましい。重合体のSP値は10.0~18.0(cal/cm3)1/2であることがより好ましく、11.5~14.0(cal/cm3)1/2であることがさらに好ましい。重合体のSP値が9.0~20.0(cal/cm3)1/2であると、電解液の吸液の点で好ましい。
被覆剤によって被覆された、被覆活物質は、例えば、活物質を万能混合機に入れて10~500rpmで撹拌した状態で、被覆用樹脂を含む樹脂溶液(被覆用樹脂溶液)を1~90分かけて滴下混合し、さらに導電助剤を混合し、撹拌したまま50~200℃に昇温し、0.007~0.04MPaまで減圧した後に、10~150分保持することにより得ることができる。なお、樹脂溶液の溶媒としては、メタノール、エタノールまたはイソプロパノールなどのアルコールが好適に使用できる。
本発明の実施形態によれば、極性の異なる2つの電極または前記電解質層に含まれる電解液が、ゲル状電解質であり、極性の異なる2つの電極における活物質層に含まれる電解液は、ゲル状電解質でありうる。かかる活物質層に、ゲル状電解質を含ませる方法にも特に制限はなく、図8の形態では、不織布60の第2主面62に、被覆活物質を含むスラリーに、ゲル状電解質も含ませてもよい。図9の形態では、導電部材213および被覆活物質を含むスラリーに、ゲル状電解質を含ませてもよい。図10の形態では、正極活物質14、導電性繊維213、樹脂214を含む活物質用組成物に、ゲル状電解質を含ませてもよい。また、上記のように作製した活物質層にゲル状電解質を含浸等して湿らせることによっても含ませることもできる。
液体電解質とゲル化剤とを、本発明の非水電解質二次電池に用いる場合と同じ比率で混合した混合物をゲル化してゲル電解質を作製する。作製したゲル電解質を用い、25℃でJIS R 1661-2004 ファインセラミックスイオン伝導体の導電率測定方法に準じて交流インピーダンス法によって測定する。
活物質層のうち少なくとも一方は、電子伝導材料からなる導電部材と、被覆活物質とを含む。電解液は、これら以外に、イオン伝導性ポリマー、支持塩等を含みうる。
イオン伝導性ポリマーとしては、例えば、ポリエチレンオキシド(PEO)系およびポリプロピレンオキシド(PPO)系のポリマーが挙げられる。
支持塩としては、例えば、LiPF6、LiBF4、LiSbF6、LiAsF6およびLiClO4等の無機酸のリチウム塩、LiN(CF3SO2)2、LiN(C2F5SO2)2およびLiC(CF3SO2)3等の有機酸のリチウム塩等が挙げられる。これらの内、電池出力および充放電サイクル特性の観点から好ましいのはLiPF6である。
本形態の電解質層17に使用される電解質は、ゲル状電解質でありうる。ゲル状電解質の説明は、上記したので、ここでは省略する。
集電板(25、27)を構成する材料は、特に制限されず、電池用の集電板として従来用いられている公知の高導電性材料が用いられうる。集電板の構成材料としては、例えば、アルミニウム、銅、チタン、ニッケル、ステンレス鋼(SUS)、これらの合金等の金属材料が好ましい。軽量、耐食性、高導電性の観点から、より好ましくはアルミニウム、銅であり、特に好ましくはアルミニウムである。なお、正極集電板27と負極集電板25とでは、同一の材料が用いられてもよいし、異なる材料が用いられてもよい。
また、図示は省略するが、集電体11と集電板(25、27)との間を正極リードや負極リードを介して電気的に接続してもよい。正極および負極リードの構成材料としては、公知のリチウムイオン二次電池において用いられる材料が同様に採用されうる。なお、外装から取り出された部分は、周辺機器や配線などに接触して漏電したりして製品(例えば、自動車部品、特に電子機器等)に影響を与えないように、耐熱絶縁性の熱収縮チューブなどにより被覆することが好ましい。
シール部(絶縁層)は、集電体同士の接触や単電池層の端部における短絡を防止する機能を有する。シール部を構成する材料としては、絶縁性、固体電解質の脱落に対するシール性や外部からの水分の透湿に対するシール性(密封性)、電池動作温度下での耐熱性等を有するものであればよい。例えば、アクリル樹脂、ウレタン樹脂、エポキシ樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリイミド樹脂、ゴム(エチレン-プロピレン-ジエンゴム:EPDM)、等が用いられうる。また、イソシアネート系接着剤や、アクリル樹脂系接着剤、シアノアクリレート系接着剤などを用いても良く、ホットメルト接着剤(ウレタン樹脂、ポリアミド樹脂、ポリオレフィン樹脂)などを用いても良い。なかでも、耐蝕性、耐薬品性、作り易さ(製膜性)、経済性等の観点から、ポリエチレン樹脂やポリプロピレン樹脂が、絶縁層の構成材料として好ましく用いられ、非結晶性ポリプロピレン樹脂を主成分とするエチレン、プロピレン、ブテンを共重合した樹脂を用いることが、好ましい。
電池外装体としては、公知の金属缶ケースを用いることができるほか、図1に示すように発電要素を覆うことができる、アルミニウムを含むラミネートフィルム29を用いた袋状のケースが用いられうる。該ラミネートフィルムには、例えば、PP、アルミニウム、ナイロンをこの順に積層してなる3層構造のラミネートフィルム等を用いることができるが、これらに何ら制限されるものではない。高出力化や冷却性能に優れ、EV、HEV用の大型機器用電池に好適に利用することができるという観点から、ラミネートフィルムが好ましい。また、外部から掛かる発電要素への群圧を容易に調整することができ、所望の電解液層厚みへと調整容易であることから、外装体はアルミネートラミネートがより好ましい。
組電池は、電池を複数個接続して構成した物である。詳しくは少なくとも2つ以上用いて、直列化あるいは並列化あるいはその両方で構成されるものである。直列、並列化することで容量および電圧を自由に調節することが可能になる。
本発明の非水電解質二次電池は、長期使用しても放電容量が維持され、サイクル特性が良好である。さらに、体積エネルギー密度が高い。電気自動車やハイブリッド電気自動車や燃料電池車やハイブリッド燃料電池自動車などの車両用途においては、電気・携帯電子機器用途と比較して、高容量、大型化が求められるとともに、長寿命化が必要となる。したがって、上記非水電解質二次電池は、車両用の電源として、例えば、車両駆動用電源や補助電源に好適に利用することができる。
撹拌機、温度計、還流冷却管、滴下ロートおよび窒素ガス導入管を付した4つ口フラスコに、酢酸エチル83部とメタノール17部とを仕込み68℃に昇温した。
LiCoO2粉末(日本化学工業(株)製 セルシードC-8G)96重量部を万能混合機に入れ、室温(25℃)、150rpmで撹拌した状態で、被覆用樹脂溶液(樹脂固形分濃度30重量%)を樹脂固形分として2重量部になるように60分かけて滴下混合し、さらに30分撹拌した。
エチレンカーボネート(EC)とジエチルカーボネート(DEC)の混合溶媒(体積比率1:1)に、LiPF6を1mol/Lの割合で溶解させて、リチウムイオン電池用電解液を作製した。
電解液1の100重量部に対して、ゲル化剤としてトリエチレングリコールジアクリレート 3.8重量部と、トリメチロールプロパントリアクリレート 1重量部とを加えてよく混合した。その後に、重合開始剤としてt-ブチルパーオキシピバレート 0.5重量部を混合することで調製した。混合して得られた混合物を80℃の恒温槽に入れて2時間熱重合し、電導度測定用の電導度を作成し、25℃に温調した後、JIS R 1661-2004 ファインセラミックスイオン伝導体の導電率測定方法に準じて交流インピーダンス法により電導度を測定した。電導度は、0.7mS/cmであった。
電解液1の100重量部に対して、ゲル化剤としてトリエチレングリコールジアクリレート 7.6重量部と、トリメチロールプロパントリアクリレート 2重量部とを加えてよく混合した。その後に、重合開始剤としてt-ブチルパーオキシピバレート 0.5重量部を混合することで調製した。実施例1と同様に、ゲル化を行った後、電導度測定用のゲル状電解質を作成し、電導度を測定した。電導度は、0.3mS/cmであった。
炭素繊維(大阪ガスケミカル(株)製 ドナカーボ・ミルド S-243:平均繊維長500μm、平均繊維径13μm:電気伝導度200mS/cm)を導電部材として準備した。
[参考例1]
正極活物質層の表面がAl集電体上にくる(つまり、正極活物質層の表面がAl集電体と接する)ように移し、負極はLi金属箔をCu集電体上に貼り付けたものを用いた。
参考例1において、電解液1を電解液2にした以外は同様にしてセルを構成した。
参考例1において、電解液1を電解液3にした以外は同様にしてセルを構成した。
上記で使用したLiCoO2を用いて、ポリフッ化ビニリデン、アセチレンブラックをそれぞれ90:5:5重量比で加えて、N-メチルピロリドンを溶剤として用いて、スラリーを調製した。これをアプリケータでAl集電体の上にLiCoO2について参考例1と同程度の塗布密度になるように塗布して、ポップレート上で乾燥して電極とした。これをΦ60mmに打ち抜くと、ヒビが入ってしまった。
45℃の恒温槽中にセルをセットして、以下の条件で、充放電サイクル耐久試験を実施し、50サイクル後の容量維持率を表1にまとめた。
11 集電体、
11a 正極側の最外層集電体、
11b 負極側の最外層集電体、
13 正極活物質層、
15 負極活物質層、
17 電解質層、
19 単電池層、
21 発電要素、
23 双極型電極、
25 正極集電板、
27 負極集電板、
29、52 ラミネートフィルム、
31 シール部、
58 正極タブ、
59 負極タブ、
14 正極活物質、
24 負極活物質、
111 正極活物質層の第1主面、
121 正極活物質層の第2主面、
211 負極活物質層の第1主面、
221 負極活物質層の第2主面、
131 導電性繊維、
16 導電助剤、
151 被覆剤、
100 正極活物質層、
213 導電性繊維、
214 樹脂、
313 樹脂、
60 不織布、
62 不織布の第2主面、
70 濾紙、
313 濾紙、
470 濾紙、
570 板、
110 正極活物質層、
50 扁平なリチウムイオン二次電池、
57 発電要素。
Claims (9)
- 集電体上に、活物質層が形成されてなる、極性の異なる2つの電極と;
前記電極の間に配置される電解質層と;
を含む発電要素を有する、非水電解質二次電池であって、
前記極性の異なる2つの電極の活物質層のうち少なくとも一方が、電子伝導材料からなる導電部材および活物質を含み、
前記活物質層が、前記電解質層側に接触する第1主面と、前記集電体側に接触する第2主面とを有し、
前記導電部材の少なくとも一部は、前記第1主面から前記第2主面までを電気的に接続する導電通路を形成しており、前記導電通路が、前記導電通路の周囲の前記活物質と接触しており、
前記活物質の表面の少なくとも一部が、被覆用樹脂および導電助剤を含む被覆剤によって被覆されており、
前記極性の異なる2つの電極または前記電解質層に含まれる電解液が、ゲル状電解質である、非水電解質二次電池。 - 前記ゲル状電解質の電導度が0.1mS/cm以上である、請求項1に記載の非水電解質二次電池。
- 前記ゲル状電解質を形成するマトリックスポリマーが、カルボン酸エステルを官能基として含む、請求項1または2に記載の非水電解質二次電池。
- 前記被覆用樹脂が、飽和吸液状態での引張破断伸び率が10%以上である、請求項1~3のいずれか1項に記載の非水電解質二次電池。
- 前記被覆用樹脂が、活性水素成分とイソシアネート成分とを反応させて得られるウレタン樹脂である、請求項1~4のいずれか1項に記載の非水電解質二次電池。
- 前記被覆用樹脂が、ビニルモノマーを必須構成単量体とする重合体で、ビニルモノマーとして、カルボキシル基を有するビニルモノマーおよび下記式(1):
CH2=C(R1)COOR2 (1)
式(1)中、R1は水素原子またはメチル基であり、R2は、炭素数1~4の直鎖のアルキル基または炭素数4~36の分岐アルキル基である、
で表されるビニルモノマーを含む、請求項1~4のいずれか1項に記載の非水電解質二次電池。 - 前記ゲル状電解質を形成するマトリックスポリマーが、少なくとも重合性基を2つ持つ分子と、重合性基を3つ持つ分子の混合物を含む電解液に、熱重合開始剤を含ませ、熱重合して電解液をゲル化することを有することによって得られる、請求項1~6のいずれか1項に記載の非水電解質二次電池。
- 集電体上に、活物質層を形成されてなる、極性の異なる2つの電極と;前記電極の間に配置される電解質層と;を含む発電要素を有する、非水電解質二次電池の製造方法であって、
前記極性の異なる2つの電極の活物質層のうち少なくとも一方に、電子伝導材料からなる導電部材および活物質を含ませ、
前記活物質層が、前記電解質層側に接触する第1主面と、前記集電体側に接触する第2主面とを有し、前記導電部材の少なくとも一部は、前記第1主面から前記第2主面までを電気的に接続する導電通路を形成しており、前記導電通路が、前記導電通路の周囲の前記活物質と接触させており、
前記活物質の表面の少なくとも一部を、被覆用樹脂および導電助剤を含む被覆剤によって被覆させており、
前記極性の異なる2つの電極または前記電解質層に含まれる電解液を、ゲル状電解質とする、非水電解質二次電池の製造方法。 - 前記ゲル状電解質を形成するマトリックスポリマーを、少なくとも重合性基を2つ持つ分子と、重合性基を3つ持つ分子の混合物を含む電解液に、熱重合開始剤を含ませ、熱重合して電解液をゲル化することを有することによって得る、請求項8に記載の製造方法。
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CN107112596B (zh) | 2019-06-28 |
US20180048023A1 (en) | 2018-02-15 |
US11063295B2 (en) | 2021-07-13 |
EP3240095A4 (en) | 2017-11-22 |
KR20170087951A (ko) | 2017-07-31 |
EP3240095B1 (en) | 2018-10-17 |
EP3240095A1 (en) | 2017-11-01 |
US20190348712A1 (en) | 2019-11-14 |
JPWO2016104679A1 (ja) | 2017-11-16 |
US10431851B2 (en) | 2019-10-01 |
KR101871134B1 (ko) | 2018-06-25 |
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