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WO2014006973A1 - Électrode destinée à des dispositifs de stockage d'énergie électrique, dispositif de stockage d'énergie électrique utilisant celle-ci, et son procédé de production - Google Patents

Électrode destinée à des dispositifs de stockage d'énergie électrique, dispositif de stockage d'énergie électrique utilisant celle-ci, et son procédé de production Download PDF

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Publication number
WO2014006973A1
WO2014006973A1 PCT/JP2013/062886 JP2013062886W WO2014006973A1 WO 2014006973 A1 WO2014006973 A1 WO 2014006973A1 JP 2013062886 W JP2013062886 W JP 2013062886W WO 2014006973 A1 WO2014006973 A1 WO 2014006973A1
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electrode
storage device
electricity storage
porous layer
binder
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PCT/JP2013/062886
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English (en)
Japanese (ja)
Inventor
岸井　豊
植谷　慶裕
愛美 松浦
由姫 加治佐
阿部　正男
大谷　彰
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日東電工株式会社
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Publication of WO2014006973A1 publication Critical patent/WO2014006973A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode for an electricity storage device, an electricity storage device using the electrode, and a method for producing the electrode, and more particularly relates to a novel electrode for an electricity storage device having high weight energy density and high rate characteristics, an electricity storage device using the electrode, and a method for producing the electrode. is there.
  • the electrode of the electricity storage device contains an active material having a function capable of inserting and removing ions.
  • the insertion / desorption of ions of the active material is also referred to as so-called doping / dedoping, and the amount of doping / dedoping per certain molecular structure is called the doping rate (or doping rate).
  • the doping rate or doping rate
  • Electrochemically it is possible to increase the capacity of a battery by using a material having a large amount of ion insertion / desorption as an electrode. More specifically, lithium secondary batteries, which are attracting attention as power storage devices, use a graphite-based negative electrode that can insert and desorb lithium ions, and about one lithium ion is inserted per six carbon atoms. -Desorption and high capacity have been achieved.
  • lithium secondary batteries a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate is used for the positive electrode, and a carbon material capable of inserting and removing lithium ions is used for the negative electrode.
  • Lithium secondary batteries that face each other in an electrolytic solution have a high energy density, and thus are widely used as power storage devices for the electronic devices described above.
  • the lithium secondary battery is a secondary battery that obtains electric energy by an electrochemical reaction, and has a drawback that the output density is low because the speed of the electrochemical reaction is low. Furthermore, since the internal resistance of the secondary battery is high, rapid discharge is difficult and rapid charge is also difficult. Moreover, since an electrode and electrolyte solution deteriorate by the electrochemical reaction accompanying charging / discharging, generally a lifetime, ie, a cycling characteristic, is not good.
  • a lithium secondary battery using a conductive polymer such as polyaniline having a dopant as a positive electrode active material is also known (see Patent Document 1).
  • a secondary battery having a conductive polymer as a positive electrode active material is an anion transfer type in which an anion is doped into the conductive polymer during charging and the anion is dedoped from the polymer during discharging. Therefore, when a carbon material that can insert and desorb lithium ions is used as the negative electrode active material, a cation-moving rocking chair type secondary battery in which cations move between both electrodes during charge and discharge cannot be configured. . That is, the rocking chair type secondary battery has the advantage that the amount of the electrolyte is small, but the secondary battery having the conductive polymer as the positive electrode active material cannot do so, and contributes to the miniaturization of the electricity storage device. I can't.
  • a cation migration type secondary battery has also been proposed.
  • a positive electrode is formed using a conductive polymer having a polymer anion such as polyvinyl sulfonic acid as a dopant, and lithium metal is used for the negative electrode (see Patent Document 2).
  • JP-A-3-129679 Japanese Patent Laid-Open No. 1-132052
  • the secondary battery is still not sufficient in performance. That is, the battery has a lower weight energy density and lower high rate characteristics than a lithium secondary battery using a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate for the positive electrode.
  • a lithium-containing transition metal oxide such as lithium manganate or lithium cobaltate for the positive electrode.
  • the present invention has been made in order to solve the above-described problems in an electricity storage device such as a conventional lithium secondary battery, and is a novel electrode for an electricity storage device having a high weight energy density and a high rate characteristic.
  • a power storage device used and a method for manufacturing the same are provided.
  • the present invention is an electrode for an electricity storage device comprising a porous layer formed on at least a part of a current collector surface, wherein the porous layer comprises at least the following (X) and (Y),
  • the first gist of the present invention is an electrode for an electricity storage device having a concavo-convex structure in which a plurality of concave portions having an average diameter of 50 to 10,000 ⁇ m are distributed.
  • (X) An active material that inserts and desorbs ions.
  • a positive electrode for an electricity storage device using the above electrode is a second summary
  • an electricity storage device in which this is a positive electrode and the negative electrode contains the following (Z) is a third summary.
  • (Z) At least one selected from a compound or metal capable of inserting / extracting ions.
  • the manufacturing method of the electrode for electrical storage devices provided with the process of carrying out the ultrasonic dispersion process of the porous layer composition which consists of an active material (X) and a binder (Y) at least, and a solvent makes a 4th summary.
  • the present inventors made extensive studies to obtain an electricity storage device having a high weight energy density and a high rate characteristic.
  • an electricity storage device in order to improve the contact ratio with the current collector to achieve high weight energy density, etc., all electrode surfaces (all surfaces as well as the surface in contact with the current collector) are flat or submicron. Only the pores are present.
  • the present inventors paid attention to the fact that the size of the recesses on the surface of the porous electrode affects battery characteristics such as high capacity density, and as a result of further research, the concavo-convex structure existing on the electrode surface.
  • a relatively large recess is formed, thereby forming an electrolytic solution reservoir capable of storing a specific amount of electrolytic solution on the electrode surface, it is surprisingly contrary to conventional technical common sense that charging / discharging of the active material is performed. It has been found that ion migration at the time can be performed smoothly, whereby an electricity storage device having a high weight energy density and a high rate characteristic can be obtained.
  • an electrode for an electricity storage device comprising a porous layer formed on at least a part of a current collector surface, wherein the porous layer is composed of at least the above (X) and (Y), If the surface of the layer is an electrode for an electricity storage device having an uneven structure in which a plurality of recesses having an average diameter of 50 to 10,000 ⁇ m are distributed, the electricity storage device using this will have excellent weight energy density and high rate characteristics. become.
  • the obtained electricity storage device is further excellent in weight energy density.
  • the active material (X) is a conductive polymer, it is possible to realize an electricity storage device that can reduce deterioration of electrodes and electrolyte.
  • the main component of the binder (Y) is an anionic polymer
  • the ion concentration in the electrolytic solution does not substantially change, so that a large amount of the electrolytic solution is not required, and the storage device is downsized. Can be realized.
  • the obtained electricity storage device can realize a high weight energy density.
  • an electricity storage device having an electrolyte layer and a positive electrode and a negative electrode provided to face each other with the electrolyte layer interposed therebetween, wherein the positive electrode is the electrode for the electricity storage device, and the negative electrode is an electricity storage device containing the following (Z) It has high performance battery characteristics. (Z) At least one selected from a compound or metal capable of inserting / extracting ions.
  • the electricity storage is more excellent in energy characteristics.
  • a device can be obtained.
  • the electrode for an electricity storage device of the present invention is an electrode 2 composed of a porous layer formed on at least a part of the surface of a current collector 1, and this electrode 2 has an uneven structure on the surface. And having a plurality of relatively large recesses having a specific average diameter.
  • the hole 2 ' indicates a hole in the porous layer.
  • the electricity storage device of the present invention has an electrolyte layer 3 and a positive electrode 2 and a negative electrode 4 provided to face each other, and the positive electrode 2 is the electrode 2 described above.
  • the negative electrode 4 includes at least one selected from a compound or metal capable of inserting / extracting ions.
  • the electrode for an electricity storage device of the present invention is a porous layer composed of at least an active material (X) for inserting / extracting ions and a binder (Y).
  • active material examples include, for example, polyacetylene, polypyrrole, polyaniline, polythiophene, polyfuran, polyselenophene, and polyisothianaphthene.
  • inorganic materials such as lithium cobaltate, lithium manganate, lithium nickelate, and lithium iron phosphate are also included.
  • polyaniline or polyaniline derivatives having a large electrochemical capacity are particularly preferably used.
  • polyaniline derivative examples include at least a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • a substituent such as an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylaryl group, an arylalkyl group, and an alkoxyalkyl group at positions other than the 4-position of the aniline.
  • o-substituted anilines such as o-methylaniline, o-ethylaniline, o-phenylaniline, o-methoxyaniline, o-ethoxyaniline, m-methylaniline, m-ethylaniline, m-methoxyaniline, m M-substituted anilines such as -ethoxyaniline and m-phenylaniline are preferably used. These may be used alone or in combination of two or more.
  • a conductive polymer material such as polyaniline is usually in a doped state (in which ions are inserted). Further, when the above (X) is not in a doped state, a doped state is obtained by performing a doping process.
  • the doping treatment include a method of mixing a dopant containing atoms to be doped into a starting material (for example, aniline), a method of reacting a product material (for example, polyaniline) with a dopant, and the like.
  • the insertion / desorption of ions in (X) is also referred to as so-called doping / dedoping.
  • the doping / dedoping amount per certain molecular structure is called the doping rate, and the doping rate is The higher the material, the higher the capacity of the battery.
  • the ions at this time are sometimes called dopants.
  • the doping rate of the conductive polymer as the X component is said to be 0.5 for polyaniline and 0.25 for polypyrrole.
  • the conductivity of the conductive polyaniline is about 10 0 to 10 3 S / cm in the doped state, and 10 ⁇ 15 to 10 ⁇ 2 S / cm in the undoped state.
  • the above (X) may be in a doped state (during discharging) during charging or discharging, or may be in a dedope state or a reduced dedoping state (during charging).
  • a dedope state is obtained by neutralizing the dopant which (X) has.
  • (X) in a dedope state is obtained by stirring in a solution for neutralizing the dopant (X) and then washing and filtering.
  • a method of neutralizing by stirring in an aqueous sodium hydroxide solution can be mentioned.
  • a reduced dedoped state is obtained by reducing (X) in the undoped state.
  • stirring in a solution for reducing (X) in the dedope state, followed by washing and filtering yields (X) in the reduced dedope state.
  • a method of reducing polyaniline in a dedoped state by stirring in an aqueous methanol solution of phenylhydrazine can be mentioned.
  • the electricity storage device of the present invention comprises an electrode using a material containing at least the above (X) and a binder (Y) described below.
  • binder (Y) examples include not only binders such as vinylidene fluoride and styrene-butadiene rubber, but also polyanions, anion compounds having a relatively large molecular weight, anionic polymers having low solubility in an electrolyte solution, and the like. can give.
  • the main component of binder (Y) consists of the said anionic polymer.
  • the main component means a component that occupies the majority of the whole, and includes the case where the whole consists of only the main component.
  • anionic polymers compounds having a carboxyl group in the molecule are preferably used, and polycarboxylic acids that are polymers in particular are more preferably used.
  • polycarboxylic acid examples include polymaleic acid, polyacrylic acid, polymethacrylic acid, polyvinylbenzoic acid, polyallylbenzoic acid, polymethallylbenzoic acid, polymaleic acid, polyfumaric acid, polyglutamic acid, and polyaspartic acid.
  • Acrylic acid and polymethacrylic acid are particularly preferably used. These may be used alone or in combination of two or more.
  • this polymer when a polymer such as the above polycarboxylic acid is used as the binder (Y), this polymer also functions as a dopant, so that it has a rocking chair type mechanism and has characteristics of the electricity storage device. It seems to be involved in improvement.
  • polycarboxylic acid examples include those in which a carboxylic acid having a carboxyl group in the molecule is converted to a lithium type.
  • the exchange rate for the lithium type is preferably 100%, but the exchange rate may be low depending on the situation, and is preferably 40% to 100%.
  • the binder (Y) is usually used in an amount of 1 to 100 parts by weight, preferably 2 to 70 parts by weight, and most preferably 5 to 40 parts by weight with respect to 100 parts by weight of the active material (X). . If the amount of the binder (Y) relative to the (X) is too small, a uniform electrode tends not to be obtained. On the other hand, even if the amount of the binder (Y) relative to the (X) is too large, the energy density is high. There is a tendency that an electricity storage device cannot be obtained.
  • the electrode according to the electricity storage device of the present invention is composed of a composite composed of at least the above (X) and (Y), and is preferably formed on a porous sheet.
  • the thickness of the electrode is preferably 1 to 500 ⁇ m, and more preferably 10 to 300 ⁇ m.
  • the thickness of the electrode is obtained by measuring the electrode using a dial gauge (manufactured by Ozaki Mfg. Co., Ltd.) whose tip shape is a flat plate having a diameter of 5 mm, and obtaining the average of 10 measured values with respect to the surface of the electrode.
  • a dial gauge manufactured by Ozaki Mfg. Co., Ltd.
  • the thickness of the composite is measured in the same manner as described above, the average of the measured values is obtained, and the thickness of the aluminum foil is subtracted.
  • the thickness of the electrode can be obtained by calculation.
  • the electrode for an electricity storage device of the present invention is formed, for example, as follows. Dissolve the binder (Y) in water to make an aqueous solution, and then add an active material (X) and, if necessary, a conductive assistant such as conductive carbon black to prepare a paste. To do. A composite having a layer of a uniform mixture of the X component and the Y component (and, if necessary, a conductive aid) on the current collector by evaporating water after applying this on the current collector As a result, a sheet electrode can be obtained.
  • the electrode for electrical storage devices of this invention consists of a porous layer, and has an uneven structure in the surface (surface which contacts electrolyte solution).
  • an electrolytic solution can be stored in the uneven structure, which is a feature of the present invention.
  • the convex part which forms the uneven structure of this invention is formed from the porous layer, and the electrolyte solution which exists in a recessed part, and the electrolyte solution in a convex porous layer may be connected by the through-hole. .
  • Such a concavo-convex structure can be formed using, for example, the following method.
  • a slurry solution is prepared by adding the active material (X) and the binder (Y) and, if necessary, a solvent, a conductive additive, etc.
  • the stirring and mixing step the slurry-like solution is maintained in a dispersion state having a constant dispersion diameter larger than usual. Specifically, each main mixing condition is controlled so as to leave a certain large and constant dispersion diameter.
  • the solvent of the slurry solution is a solvent having relatively low solubility in the binder
  • a porous layer having a relatively large dispersion diameter can be obtained when it is applied onto the current collector and dried. Therefore, a concavo-convex structure resulting from the dispersion diameter is formed on the surface of the porous layer.
  • the average diameter of the concavo-convex structure is 50 to 10,000 ⁇ m.
  • the average diameter is preferably 100 to 10,000 ⁇ m, more preferably 500 to 5,000 ⁇ m.
  • the average diameter is measured as follows. First, the produced electrode is cut in the thickness direction to produce a measurement sample. A tomographic image is constructed by X-ray CT, a plurality of distances between convex portions of 50 ⁇ m or more are obtained, and the average value is taken as the average diameter. In addition, when only the convex part less than 50 micrometers exists, a scanning electron microscope (SEM) observation is performed and an average diameter is calculated
  • SEM scanning electron microscope
  • the recess is formed on the surface of the porous layer, and the average diameter of the recess is 50 to 10,000 ⁇ m, whereas the average diameter of the pores of the porous layer is less than 5 ⁇ m, Obviously different.
  • the present invention has a relatively large number of concave portions distributed, and this is a considerable amount of electrolyte solution. It is a liquid reservoir that can store water.
  • the liquid pool ratio of the recesses on the electrode surface is preferably 3 to 70%, more preferably 5 to 50%, and still more preferably 10 to 30%. If the liquid pool rate is too small, the contact surface between the electrode and the electrolytic solution decreases, so that it tends to be difficult to achieve a high energy density or the like. If it is too large, the amount of active material in the electrode is insufficient. This is because it tends to be difficult to achieve high energy density and the like.
  • liquid pool rate on the electrode surface is expressed by the following formula (1) and will be described below with reference to FIG.
  • Liquid pool ratio (%) (T 1 ⁇ T 2 ) / T 1 ⁇ 1/100 (1)
  • T 1 is the surface contact average thickness (T 1 in FIG. 3)
  • T 2 is the point contact average thickness (T 2 in FIG. 3).
  • T 1 surface contact average thickness
  • An electrode size of 70 mm (horizontal) ⁇ 140 mm (vertical) is measured at 78 points at 10 mm intervals. From the average value of the obtained values, the current collector thickness is subtracted to obtain the coating film thickness (T 1 ). Normally the coating thickness using T 1.
  • T 2 point contact average thickness
  • a spherical measuring element with a tip of the tip of the carbide contacting the electrode upper surface and the lower surface of 2 mm in diameter and a radius of curvature of 20 mm at the tip, and a measuring pressure of 0.40 N.
  • a (40 gf) sheet thickness measuring device manufactured by Mitutoyo Corporation
  • 78 points of thickness are measured as described above.
  • a value obtained by subtracting the current collector thickness from the average value of the obtained values is defined as a coating film thickness (T 2 ).
  • the liquid pool ratio (%) of the present invention can be obtained.
  • the electrode formed as described above can be used as the positive electrode of the electricity storage device of the present invention.
  • the electrolyte layer according to the power storage device of the present invention is configured using an electrolyte material.
  • a sheet obtained by impregnating a separator with an electrolytic solution or a sheet formed of a solid electrolyte is preferably used.
  • the sheet made of the solid electrolyte itself also serves as a separator.
  • the electrolyte layer material is composed of a solute (electrolyte), a solvent as necessary, and various additives.
  • solutes include metal ions such as lithium ions and appropriate counter ions, sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bis ions.
  • metal ions such as lithium ions and appropriate counter ions
  • sulfonate ions such as lithium ions and appropriate counter ions
  • perchlorate ions such as sulfonate ions, perchlorate ions, tetrafluoroborate ions, hexafluorophosphate ions, hexafluoroarsenic ions, bis ions.
  • electrolyte examples include LiCF 3 SO 3 , LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiCl. Etc.
  • the solvent used as necessary for example, at least one non-aqueous solvent such as carbonates, nitriles, amides, ethers, that is, an organic solvent is used.
  • organic solvents include ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, acetonitrile, propionitrile, N, N'-dimethylacetamide, N-methyl-2- Examples include pyrrolidone, dimethoxyethane, diethoxyethane, and ⁇ -butyrolactone. These may be used alone or in combination of two or more. In addition, what melt
  • the separator can be used in various modes.
  • the separator it is possible to prevent an electrical short circuit between the positive electrode and the negative electrode that are arranged to face each other across the separator.
  • the separator is electrochemically stable, has a large ion permeability, and has a certain level. Any insulating porous sheet having mechanical strength may be used. Therefore, as the material of the separator, for example, a porous film made of a resin such as paper, nonwoven fabric, polypropylene, polyethylene, or polyimide is preferably used. These may be used alone or in combination of two or more.
  • the negative electrode in the electricity storage device according to the present invention is formed using at least one of a metal or a compound capable of inserting / extracting ions or a metal (hereinafter also referred to as “negative electrode active material”) (Z).
  • a metal or a compound capable of inserting / extracting ions or a metal hereinafter also referred to as “negative electrode active material”) (Z).
  • metallic lithium a carbon material in which lithium ions can be inserted / extracted during oxidation / reduction, a transition metal oxide, silicon, tin, or the like is preferably used.
  • “use” means not only the case where only the forming material is used, but also the case where the forming material is used in combination with another forming material. Is used at less than 50% by weight of the forming material.
  • the thickness of the negative electrode preferably conforms to the thickness of the positive electrode.
  • the battery is preferably assembled in a glove box under an inert gas atmosphere such as ultra-high purity argon gas.
  • metal foils and meshes such as nickel, aluminum, stainless steel, and copper are appropriately used as current collectors (1, 5 in FIG. 2) for positive electrode 2 and negative electrode 4. Then, the current collectors 1 and 5 are connected to the current extraction connecting terminals (tab electrodes, not shown) of the positive electrode 2 and the negative electrode 4 using a spot welder.
  • the positive electrode 2 and the current collector 1 are vacuum-dried. Thereafter, a negative electrode active material such as a metal lithium foil is pressed against the stainless steel mesh in a glove box having a dew point of ⁇ 100 ° C. to produce a composite of the negative electrode 4 and the current collector 5.
  • a negative electrode active material such as a metal lithium foil is pressed against the stainless steel mesh in a glove box having a dew point of ⁇ 100 ° C. to produce a composite of the negative electrode 4 and the current collector 5.
  • a predetermined number of various separators (not shown) are sandwiched between the positive electrode 2 and the negative electrode 4 in the glove box, and the positive electrode 2 and the negative electrode 4 are placed in a laminate cell heat-sealed on these three sides. Adjust the position of the separator so that they face each other correctly and do not short-circuit.
  • the tab electrode portion is heat-sealed, leaving a little electrolyte inlet. Thereafter, a predetermined amount of battery electrolyte is sucked with a micropipette, and a predetermined amount is injected from the electrolyte solution inlet of the laminate cell. Finally, the electrolyte solution inlet at the top of the laminate cell is sealed by heat sealing to complete the electricity storage device (laminate cell) of the present invention.
  • the electricity storage device of the present invention is formed into various shapes such as a film type, a sheet type, a square type, a cylindrical type, and a button type in addition to the laminate cell.
  • the positive electrode size of the electricity storage device is preferably 1 to 300 mm on one side in the case of a laminate cell, particularly preferably 10 to 50 mm, and the electrode size of the negative electrode is 1 to 400 mm. It is preferably 10 to 60 mm.
  • the electrode size of the negative electrode is preferably slightly larger than the positive electrode size.
  • conductive polyaniline powder using tetrafluoroboric acid as a dopant was prepared as follows.
  • the powder means a collection of particles.
  • aniline When aniline was added to the tetrafluoroboric acid aqueous solution, the aniline was dispersed as oily droplets in the tetrafluoroboric acid aqueous solution, but then dissolved in water within a few minutes, and the uniform and transparent aniline aqueous solution. Became.
  • the aniline aqueous solution thus obtained was cooled to ⁇ 4 ° C. or lower using a low temperature thermostat.
  • the reaction mixture containing the produced reaction product was further stirred for 100 minutes while cooling. Then, using a Buchner funnel and a suction bottle, the obtained solid was No. Suction filtration was performed with two filter papers (manufactured by ADVANTEC) to obtain a powder. This powder was stirred and washed in a 2 mol / L tetrafluoroboric acid aqueous solution using a magnetic stirrer. Subsequently, it was stirred and washed several times with acetone, and this was filtered under reduced pressure.
  • conductive polyaniline having tetrafluoroboric acid as a dopant
  • the conductive polyaniline was a bright green powder.
  • Binder 1 solution aqueous solvent
  • polyacrylic acid manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000,000
  • 0.15 g of lithium hydroxide was added and dissolved again to prepare a polyacrylic acid-polylithium acrylate complex solution (binder 1 solution) in which 50% of the acrylic acid sites were replaced with lithium.
  • Binder 2 solution water / methanol mixed solvent
  • polyacrylic acid manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000,000
  • this was heated and stirred to dissolve in a water / methanol mixed solvent (weight ratio 1/1), and a uniform concentration of 4.4 wt% 20.5 g of a viscous polyacrylic acid aqueous solution was obtained.
  • 0.15 g of lithium hydroxide was added and dissolved again to prepare a polyacrylic acid-polylithium acrylate complex solution (binder 2 solution) in which 50% of the acrylic acid sites were replaced with lithium.
  • a non-woven fabric (manufactured by Hosen Co., Ltd., TF40-50 (porosity: 55%)) was prepared.
  • Example 1 ⁇ Forming a positive electrode using (X) and (Y)> After mixing 4 g of reduced dedope polyaniline powder prepared as X component, 0.5 g of conductive carbon black (Denka Black, Denki Kagaku Kogyo Co., Ltd.) and 4 g of water, this was prepared as described above. It was added to 20.5 g of the binder 1 solution and kneaded well with a spatula. This was subjected to ultrasonic treatment for 5 minutes with an ultrasonic homogenizer, and a paste having fluidity was obtained using a Fillmix 40-40 type (manufactured by Primix). The paste was further defoamed for 3 minutes with Awatori Nertaro (Sinky Corp.) to obtain a defoamed paste.
  • conductive carbon black Denki Kagaku Kogyo Co., Ltd.
  • the solution coating thickness was adjusted to 360 ⁇ m with a doctor blade type applicator with a micrometer, and the above defoamed paste was removed at a coating speed of 10 mm / second. It apply
  • the battery was assembled in a glove box under an ultra-high purity argon gas atmosphere (dew point in the glove box: ⁇ 100 ° C.).
  • the electrode size of the positive electrode for the laminate cell is 27 mm ⁇ 27 mm, the negative electrode size is 29 mm ⁇ 29 mm, which is slightly larger than the positive electrode size.
  • the metal foils of the positive electrode and negative electrode tab electrodes were respectively connected to the corresponding metal foils of current collectors using a spot welder.
  • a positive electrode, a negative electrode, and a separator on which a tab electrode was previously attached by a spot welder were vacuum dried at 80 ° C. for 2 hours. After that, it was put in a glove box with a dew point of ⁇ 100 ° C., and the prepared metal lithium foil was pressed into the stainless steel mesh of the current collector in the glove box to make a composite of the negative electrode and the current collector. .
  • Example 2 A polyaniline sheet electrode was obtained in the same manner as in Example 1 except that the defoamed paste prepared in Example 1 was further subjected to ultrasonic treatment with an ultrasonic homogenizer for 1 minute, and then a lithium secondary battery was produced. .
  • Example 3 After 4 g of the conductive polyaniline powder was mixed with 0.5 g of conductive carbon black powder (Denka Black, manufactured by Denki Kagaku Kogyo Co., Ltd.), this was added to 20.5 g of the prepared binder 2 solution and kneaded well with a spatula. Thereafter, ultrasonic treatment was performed for 5 minutes with an ultrasonic homogenizer, and then a paste having fluidity was obtained using a Fillmix 40-40 type (manufactured by Primix). This paste was defoamed for 3 minutes with Awatori Nertaro (Sinky Corp.) to obtain a defoamed paste. Except for the preparation of this defoaming paste, a polyaniline sheet electrode was obtained by the same operation as in Example 1, and then a lithium secondary battery was produced.
  • conductive carbon black powder Denki Kagaku Kogyo Co., Ltd.
  • a lithium secondary battery was produced in the same manner as in Example 1 except that the positive electrode produced above was used in place of the polyaniline sheet electrode of Example 1.
  • Porosity of electrode (%) ⁇ (apparent volume of electrode ⁇ true volume of electrode) / apparent volume of electrode ⁇ ⁇ 100
  • the apparent volume of the electrode means “the electrode area of the electrode ⁇ the electrode thickness excluding the aluminum foil that is the current collector”.
  • the true volume of the electrode means “the volume of the electrode constituent material excluding the aluminum foil”. Specifically, as described above, using the constituent weight ratio of the electrode constituent material and the true density value of each constituent material, the average density of the entire electrode constituent material is calculated, and the total weight of the electrode constituent material is calculated. It is obtained by dividing by this average density.
  • the discharge capacity retention rate (%) is obtained by charging and discharging at 0.2 C in a constant current / constant voltage charge / constant current discharge mode using a battery charge / discharge device (Hokuto Denko, SD8). Further, charging / discharging at 10 C was performed to determine the discharge capacity. The value obtained by the following formula (3) was defined as the discharge capacity retention rate (%).
  • Discharge capacity retention rate (%) discharge capacity at 10 C / discharge capacity at 0.2 C ⁇ 100 (3)
  • 0.2C means a current value at which charging or discharging is completed after 5 hours of constant current charging or discharging using the assembled secondary battery
  • 10C is It means a current value at which charging or discharging is completed in 6 minutes after constant current charging or discharging.
  • the electrode of this example product in which a plurality of recesses having an average diameter of 50 to 10,000 ⁇ m are distributed has a charge efficiency and a discharge capacity maintenance rate that are higher than those of the comparative example. It was found to have high rate performance. Moreover, it turned out that any Example has a high weight energy density except the comparative example 1.
  • the electricity storage device of the present invention can be suitably used as an electricity storage device such as a lithium secondary battery.
  • the power storage device of the present invention can be used for the same applications as conventional secondary batteries.
  • portable electronic devices such as portable PCs, mobile phones, and personal digital assistants (PDAs), hybrid electric vehicles, Widely used in power sources for driving automobiles, fuel cell vehicles and the like.

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

Abstract

Afin d'obtenir un nouveau dispositif de stockage d'énergie électrique qui est doté d'une densité d'énergie mesurée élevée et de caractéristiques de débit élevé, la présente invention a trait à une électrode destinée à des dispositifs de stockage d'énergie électrique, laquelle électrode est pourvue d'une couche poreuse (2) qui est formée sur au moins une partie de la surface d'un collecteur (1). La couche poreuse est constituée au moins des composants (X) et (Y) décrits ci-dessous, et la surface de la couche poreuse est constituée d'une structure en retrait et en saillie où une pluralité d'évidements qui sont dotés d'un diamètre moyen de 50 à 10 000 μm est distribuée. (X) une matière active qui intercale les ions et supprime l'intercalation de ces derniers (Y) un liant
PCT/JP2013/062886 2012-07-04 2013-05-08 Électrode destinée à des dispositifs de stockage d'énergie électrique, dispositif de stockage d'énergie électrique utilisant celle-ci, et son procédé de production WO2014006973A1 (fr)

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JP2012150781A JP2014013702A (ja) 2012-07-04 2012-07-04 蓄電デバイス用電極、それを用いた蓄電デバイスおよびその製法
JP2012-150781 2012-07-04

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109997262A (zh) * 2016-11-25 2019-07-09 出光兴产株式会社 电化学元件用粘结剂
CN110247022A (zh) * 2019-06-24 2019-09-17 陈志勇 一种smt贴片电池和极片以及该电池和极片的制作方法
CN112563443A (zh) * 2020-11-20 2021-03-26 扬州大学 一种柔性电池电极及其制作工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10172537A (ja) * 1996-12-17 1998-06-26 Mitsubishi Electric Corp リチウムイオン二次電池及びその製造方法
JP2005108521A (ja) * 2003-09-29 2005-04-21 Hitachi Maxell Ltd 薄膜電極とその製造方法およびその薄膜電極を用いたリチウム二次電池
JP2006012576A (ja) * 2004-06-25 2006-01-12 Shin Etsu Chem Co Ltd 非水電解質二次電池用電極及びその作製方法
JP2008016581A (ja) * 2006-07-05 2008-01-24 Ricoh Elemex Corp 蓄電デバイス用電極およびその製造方法、ならびに蓄電デバイス

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10172537A (ja) * 1996-12-17 1998-06-26 Mitsubishi Electric Corp リチウムイオン二次電池及びその製造方法
JP2005108521A (ja) * 2003-09-29 2005-04-21 Hitachi Maxell Ltd 薄膜電極とその製造方法およびその薄膜電極を用いたリチウム二次電池
JP2006012576A (ja) * 2004-06-25 2006-01-12 Shin Etsu Chem Co Ltd 非水電解質二次電池用電極及びその作製方法
JP2008016581A (ja) * 2006-07-05 2008-01-24 Ricoh Elemex Corp 蓄電デバイス用電極およびその製造方法、ならびに蓄電デバイス

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109997262A (zh) * 2016-11-25 2019-07-09 出光兴产株式会社 电化学元件用粘结剂
CN110247022A (zh) * 2019-06-24 2019-09-17 陈志勇 一种smt贴片电池和极片以及该电池和极片的制作方法
CN110247022B (zh) * 2019-06-24 2021-03-23 陈志勇 一种smt贴片电池和极片以及该电池和极片的制作方法
CN112563443A (zh) * 2020-11-20 2021-03-26 扬州大学 一种柔性电池电极及其制作工艺
CN112563443B (zh) * 2020-11-20 2022-08-12 扬州大学 一种柔性电池电极及其制作工艺

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