WO2013099520A1 - Mélange d'électrode positive, électrode positive, et batterie secondaire à électrolyte non aqueux mettant en œuvre celle-ci - Google Patents

Mélange d'électrode positive, électrode positive, et batterie secondaire à électrolyte non aqueux mettant en œuvre celle-ci Download PDF

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Publication number
WO2013099520A1
WO2013099520A1 PCT/JP2012/081151 JP2012081151W WO2013099520A1 WO 2013099520 A1 WO2013099520 A1 WO 2013099520A1 JP 2012081151 W JP2012081151 W JP 2012081151W WO 2013099520 A1 WO2013099520 A1 WO 2013099520A1
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Prior art keywords
positive electrode
electrode mixture
active material
positive
surfactant
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PCT/JP2012/081151
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English (en)
Japanese (ja)
Inventor
義和 大胡
文崇 加藤
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太陽ホールディングス株式会社
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Application filed by 太陽ホールディングス株式会社 filed Critical 太陽ホールディングス株式会社
Priority to KR1020147020659A priority Critical patent/KR20140116143A/ko
Priority to CN201280064831.4A priority patent/CN104025350A/zh
Priority to JP2013551551A priority patent/JP6055782B2/ja
Publication of WO2013099520A1 publication Critical patent/WO2013099520A1/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
    • H01M4/139—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/34—Gastight accumulators
    • H01M10/345—Gastight metal hydride accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the positive electrode mixture, and more specifically, to dispersibility of a positive electrode active material, storage stability, and coating property when applied to a current collector.
  • the electrode of the secondary battery is composed of an active material, a conductive assistant, and a binder resin that binds these to a current collector.
  • the binder resin for secondary batteries is required to be flexible enough to withstand the swelling and shrinkage of the electrode.
  • both the positive electrode and the negative electrode have many fluorine resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE). Has been used.
  • a general fluororesin has insufficient adhesion to the current collector, and therefore cannot satisfy the demand for further improvement of the charge / discharge cycle life.
  • the current collector and electrode are used during battery manufacture and during battery use because the binding force with the current collector or filler (positive electrode active material and conductive additive) is weak. Separation of the mixture occurred and the internal resistance of the battery increased.
  • Patent Document 1 proposes a copolymer of vinylidene fluoride and a polar monomer such as a monoester of an unsaturated dibasic acid as a fluororesin that is a binder resin. According to this, it is possible to improve the binding property between the fluororesin and the current collector.
  • Patent Documents 2 and 3 disclose, as binder resins for negative electrode active materials, water-dispersed emulsions of styrene-butadiene copolymer (SBR) particles, and sodium or ammonium salts of SBR particles and carboxymethylcellulose (CMC).
  • SBR styrene-butadiene copolymer
  • CMC carboxymethylcellulose
  • Patent Document 4 a cross-linking agent is added to an acrylic resin as a binder resin dissolved in a solvent, and the acrylic resin and the cross-linking agent are reacted in the heating and pressure-bonding steps during electrode preparation to produce a three-dimensional cross-linked structure.
  • a technique for preventing the active material and the conductive agent from falling off during charging and discharging of the secondary battery there has been proposed a technique for preventing the active material and the conductive agent from falling off during charging and discharging of the secondary battery.
  • Patent Document 5 the surface of the positive electrode active material having an average particle size of 0.01 to 0.5 ⁇ m is coated with a surfactant to increase the surface area of the positive electrode active material subjected to the reaction, and the positive electrode A technique for preventing the aggregation of the active material and increasing the output of the secondary battery has been proposed.
  • the fluorine-based resin proposed in Patent Document 1 still has sufficient solvent resistance and chemical resistance in consideration of use under severe conditions such as when used as a binder resin for non-aqueous secondary battery electrodes. It is hard to say that you have sex.
  • the binder resin described in Patent Documents 2 and 3 although the SBR particles have the advantage that the negative electrode active material is not easily dropped even after repeated charge and discharge, a battery having a large capacity is obtained. There is a problem that can not be. Further, the SBR particles tend to be adsorbed on the carbon material that is the negative electrode active material, and tend to cover the surface of the carbon material. Therefore, the electrolyte containing lithium ions is difficult to permeate and sufficient electrical characteristics may not be obtained.
  • Patent Document 4 when the solvent-soluble binder resin proposed in Patent Document 4 is used, if the organic solvent is removed after applying the resin solution to the electrode substrate, the surface of the electrode active material is covered with the resin without any gaps. . Therefore, there is a problem that sufficient electrical characteristics cannot be obtained. Furthermore, the secondary battery proposed in Patent Document 5 has a problem that the binding of the positive electrode active material tends to be hindered and the durability of the positive electrode active material mixture layer is not sufficient.
  • Patent Documents 1 and 4 a fluororesin is used as the binder resin. However, since the fluororesin swells and dissolves only in a specific solvent such as N-methylpyrrolidone, the human body and environment such as a strange odor at the time of electrode preparation are used. Is a problem.
  • an object of the present invention is to provide excellent dispersion properties, storage stability, and coating properties when applied to a current collector, and after application to the current collector, the current collector and the positive electrode.
  • An object of the present invention is to provide a water-based positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the same, which can obtain a positive electrode having excellent adhesion to an active material.
  • the present inventors have used a surfactant as a positive electrode mixture and a specific polymer material as a water-dispersible polymer binder resin so that the positive electrode active material can be used in a solvent. Almost and uniformly dispersed, and the obtained positive electrode mixture has excellent coating properties when applied to a current collector, and the positive electrode obtained by drying the positive electrode mixture has a positive electrode mixture layer and a current collector plate As a result, the present invention has been completed.
  • the present inventor adds a surfactant having specific physical properties to the positive electrode mixture, so that the positive electrode active material is easily and uniformly dispersed in the solvent, and the obtained positive electrode mixture is a current collector. It was found that the positive electrode obtained by drying this was excellent in the adhesion between the positive electrode mixture layer and the current collector plate.
  • the positive electrode mixture of the present invention is characterized by containing a positive electrode active material, a water-dispersible polymer binder resin, a conductive auxiliary agent, and a surfactant.
  • the HLB value of the surfactant is preferably 13.0 to 20.0. Moreover, in the positive mix of this invention, it is preferable that water is included as a solvent.
  • the positive electrode of the present invention is characterized in that the positive electrode mixture of the present invention is applied to a current collector.
  • nonaqueous electrolyte secondary battery of the present invention is characterized by using the positive electrode of the present invention.
  • the positive electrode active material is excellent in dispersibility, storage stability, and coating property when applied to the current collector, and after being applied to the current collector, the current collector and the positive electrode active material.
  • An aqueous positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery using the same can be provided.
  • the positive electrode mixture of the present invention contains a positive electrode active material, a water-dispersible polymer binder resin, a conductive additive, and a surfactant.
  • a surfactant By adding a surfactant to the positive electrode mixture, the positive electrode active material and the water-dispersible polymer binder resin can be uniformly dispersed in an aqueous solvent in a short time.
  • the positive electrode active material and the water-dispersible polymer binder resin are less likely to agglomerate and settle, the applicability to the current collector is also improved.
  • the positive electrode using the positive electrode mixture of the present invention is excellent in adhesion and flexibility with the current collector and the positive electrode active material. Furthermore, the non-aqueous electrolyte secondary battery using the obtained positive electrode can suppress a decrease in discharge capacity in a charge / discharge cycle even under a high temperature environment due to repeated charging and discharging and heat generation, and has a long life. A secondary battery can be obtained.
  • each component of the positive electrode mixture of the present invention and the production method thereof will be described in detail.
  • transition metal oxides transition metal sulfides, lithium-containing composite metal oxides, and the like can be used as the positive electrode active material.
  • the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
  • the transition metal oxide include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O 5 , V 6 O 13 and the like can be suitably used.
  • MnO, V 2 O 5 , V 6 O 13 , and TiO 2 are preferable from the viewpoint of cycle stability and capacity.
  • the transition metal sulfide TiS 2 , TiS 3 , amorphous MoS 2 , FeS, or the like can be suitably used.
  • the structure of the lithium-containing composite metal oxide is not particularly limited, but a layered structure, a spinel structure, an olivine structure, or the like can be preferably used.
  • lithium-containing composite metal oxide having a layered structure examples include lithium-containing composite oxides mainly composed of lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn composite oxide.
  • lithium-containing composite metal oxides mainly composed of lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), and Co—Ni—Mn composite oxide.
  • lithium-containing composite metal oxide having a spinel structure examples include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (wherein M may include Cr, Fe, Co, Ni, Cu and the like.
  • Li X MPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, lithium-containing composite metal oxide having an olivine structure)
  • An olivine type lithium phosphate compound represented by at least one selected from Si, B and Mo, 0 ⁇ X ⁇ 2) can be given.
  • LiFePO 4 and LiCoPO 4 are often used by being atomized because of their low conductivity, and since these have many pores, they have a large surface area and are compatible with a resin that serves as a binder. Is bad.
  • the positive electrode mixture of the present invention contains a surfactant, LiFePO 4 and LiCoPO 4 can be preferably used.
  • the positive electrode active material those having an average particle diameter of 0.01 ⁇ m or more and less than 50 ⁇ m can be preferably used, and more preferably 0.1 ⁇ m to 30 ⁇ m. If the particle size is within the above range, the amount of the water-dispersible polymer binder resin can be reduced, the decrease in battery capacity can be suppressed, the aggregation of the positive electrode active material can be prevented, and the positive electrode mixture can be dispersed. A uniform electrode can be obtained with good properties.
  • the particle diameter is the maximum distance L among any two points on the particle outline, and the average particle diameter is a scanning electron microscope (SEM) or a transmission electron microscope. This is a value calculated as an average value of particle diameters of particles observed in several to several tens of fields using an observation means such as (TEM).
  • the positive electrode active material when an iron-based oxide having poor electrical conductivity is used as the positive electrode active material, it can be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to exist during reduction firing. These carbon source materials may be partially element-substituted.
  • the positive electrode active material for a non-aqueous electrolyte secondary battery may be a mixture of the above inorganic compound and an organic compound that is a conductive polymer such as polyacetylene or poly-p-phenylene.
  • the water-dispersible polymer binder resin is a polymer binder resin that can be dispersed in an aqueous solvent described later.
  • water-dispersible polymer binder resins include non-fluorine polymers such as vinyl polymers, acrylic polymers, nitrile polymers, polyurethane polymers, and diene polymers, and fluorine-based polymers such as PVDF and PTFE. A polymer can be mentioned.
  • a non-fluorinated polymer is preferable from the viewpoint of adhesiveness to a current collector or a positive electrode mixture, and more preferably an acrylic resin or a weight average molecular weight of at least a polyol and a polyisocyanate is 8,000 to 1. 500,000, preferably a polyurethane resin having a weight average molecular weight of 10,000 to 1,000,000.
  • an acrylic resin is used as the water-dispersible polymer resin binder
  • an acrylic resin or methacrylic acid ester and a copolymer of other functional monomers may be used.
  • a polyurethane resin is used as the water-dispersible polymer resin binder, if the weight average molecular weight is less than 8,000, the durability of the binder may be lowered, while the weight average molecular weight is 1,500,000. If it exceeds, the durability of the binder is improved, but the binder itself aggregates, and the dispersibility and coatability may be significantly reduced.
  • the particle size is preferably 0.05 to 5 ⁇ m, more preferably 0.1 to 1 ⁇ m. If the particle diameter exceeds 5 ⁇ m, the binding property may be lowered.
  • the particle diameter is less than 0.05 ⁇ m, the surface of the positive electrode active material may be covered and the internal resistance may be increased.
  • combination of the said polyurethane resin A well-known thing can be used.
  • limiting in particular as said acrylic resin A well-known thing can be used.
  • combination of the said acrylic resin A known thing can be used.
  • the polyurethane resin or acrylic resin may be used in the form of an aqueous emulsion or an aqueous dispersion.
  • a known method can be adopted, for example, a surfactant method using a surfactant such as soap, an emulsification such as a colloid method using a water-soluble polymer such as polyvinyl alcohol as a protective colloid. It may be produced by polymerization, and a batch polymerization method, a pre-emulsion dropping method, a monomer dropping method, or the like may be used. Moreover, the average particle diameter of the various polymers in the aqueous emulsion can be changed by controlling the monomer concentration, reaction temperature, stirring speed, and the like. By emulsion polymerization, the particle size distribution of the polymer can be sharpened, and by using such an aqueous emulsion, various components in the electrode can be made homogeneous.
  • a polytetrafluoroethylene-based aqueous dispersion can be suitably used.
  • a well-known method can be employ
  • Polyester polyols can be suitably used as the polyol used for the synthesis of the polyurethane resin according to the positive electrode mixture of the present invention.
  • the polyester polyols include polyester polyol, polyester polycarbonate polyol, and polycarbonate polyol.
  • polyester polyols are preferable when a polyurethane resin is used as a binder resin because good durability and strength are provided.
  • the polyester polyol is a direct esterification reaction between a low-molecular polyhydric alcohol and a polycarboxylic acid having an amount less than the stoichiometric amount of the low-molecular polyhydric alcohol or an ester-forming derivative such as an ester, an anhydride or a halide thereof. And / or what can be obtained by transesterification can be mentioned.
  • low molecular weight polyhydric alcohol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3- Propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octane Diol, 2-methyl-1,8-octanediol, 1,9-nonaned
  • polycarboxylic acids or ester-forming derivatives thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, Aliphatic dicarboxylic acids such as dimer acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, trimellitic acid, trimesic acid, castor oil fatty acid
  • the polyisocyanate used for the synthesis of the polyurethane resin according to the positive electrode mixture of the present invention is not particularly limited, and a known polyisocyanate can be used.
  • a known polyisocyanate can be used.
  • the polyisocyanate a mixture of diisocyanate and triisocyanate is preferable because the resulting polyurethane resin has good dispersibility and is inexpensive.
  • diisocyanate examples include 2,4- and / or 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3.
  • Aromatic diisocyanates such as' -dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexyl diisocyanate, Cycloaliphatic diisocyanates such as norbornene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 (2,4,4) -trimethylhexamethyle Diisocyanate, and aliphatic diisocyanates such as lysine diisocyanate.
  • alicyclic diisocyanates are preferred because they are excellent in hydrolysis resistance. These may be used singly or in combination of two or more.
  • triisocyanate examples include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, isocyanurate trimerization, burette trimerization, trimethylolpropane adducts of the above-mentioned diisocyanates. It can.
  • isocyanurate trimers are preferred because they give a stable dispersion to the polyurethane resin. These may be used singly or in combination of two or more.
  • a polyurethane resin polymerized using a chain extender may be used as the polyurethane resin. That is, when a high molecular weight polyurethane resin is required, a known chain extender used for the synthesis of a polyurethane resin can be used. As the chain extender, a polyvalent amine compound, a polyvalent primary alcohol compound and the like are preferable, and a polyvalent amine compound is more preferable.
  • polyvalent amine compound examples include low molecular weight polyamines in which the alcoholic hydroxyl group of the above exemplified low molecular polyol such as ethylenediamine and propylenediamine is substituted with an amino group, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine , Polyether polyamines such as polyoxypropylenetriamine, mensendiamine, isophoronediamine, norbornenediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminomethyl Piperazine, alicyclic polyamines such as 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane, m-xylenediamine, ⁇ (M / p aminophenyl)
  • the production method of the polyurethane resin according to the positive electrode mixture of the present invention is not particularly limited, and a known production method can be used.
  • a prepolymer method is preferred in which a polyol, diisocyanate and triisocyanate are reacted together to prepare a urethane prepolymer in advance and the chain can be extended in water in the presence of a chain extender.
  • the amount of the chain extender is not particularly limited, and any amount can be selected and used.
  • the isocyanate group in the prepolymer is preferably from 0.1 to 1.5, since the resulting water-dispersible polyurethane composition has good dispersibility and does not discolor, and is preferably 0.5 to 1. 0 is more preferable.
  • acrylic ester and methacrylic ester used for the synthesis of the acrylic resin according to the positive electrode mixture of the present invention include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid-n-propyl, methacrylic acid.
  • a functional monomer can be added in addition to the acrylic ester and the methacrylic ester.
  • monofunctional monomers include styrene, ⁇ -methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, Aromatic vinyl monomers such as 4- (phenylbutyl) styrene and halogenated styrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; butadiene, isoprene, 2,3-dimethylbutadiene, 2-methyl-3-ethyl Butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-p
  • multifunctional monomer examples include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, diallyl malate, divinyl adipate, divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate.
  • the production method of the acrylic resin according to the present invention is not particularly limited, and a known production method can be used.
  • polymer particles may be added to the water-dispersible polymer binder resin as necessary.
  • polymer particles include non-fluorine polymers such as vinyl polymers, acrylic polymers, nitrile polymers, polyurethane polymers, and diene polymers; fluorine polymers such as PVDF and PTFE; In particular, a non-fluorine polymer is preferable from the viewpoint of adhesiveness.
  • these polymer particles may be used alone or in combination of two or more.
  • the content of the water-dispersible polymer binder resin is preferably 0.1 to 10 parts by mass in solid content with respect to 100 parts by mass of the positive electrode active material. More preferably, it is 0.5 to 5 parts by mass.
  • the average particle size of the water-dispersible polymer binder resin is preferably 0.05 to 5 ⁇ m, more preferably 0.1 to 1 ⁇ m. If the particle size is too large, the binding property may decrease, and if the particle size is too small, the surface of the positive electrode active material may be covered and the internal resistance may be increased.
  • ⁇ Conductive aid> In the positive electrode mixture of the present invention, as the conductive assistant, acetylene black, ketjen black, carbon black, graphite, vapor grown carbon fiber, and conductive carbon such as carbon nanotube, graphene, fullerene can be used. .
  • a conductive additive By using a conductive additive, the electrical contact between the positive electrode active materials can be improved, and when used in a non-aqueous electrolyte secondary battery, the discharge rate characteristics can be improved.
  • the blending amount of the conductive assistant is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the surfactant is particularly limited as long as it has high dispersibility in the electrolyte, low reactivity with lithium ions, etc., and does not hinder ion conduction in the electrolyte. is not.
  • examples of the surfactant include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant, and it is particularly preferable to use a nonionic surfactant. . This is because the nonionic surfactant has low reactivity with surrounding ions (such as lithium ions) and does not hinder ion conduction in the electrolyte and on the active material surface.
  • the surfactant may be used alone or in combination of two or more.
  • Examples of the cationic surfactant include mono / di long chain alkyl type quaternary ammonium salts, alkylamine salts, and the like.
  • Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, alkenyl ether sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid or ester salt thereof.
  • Alkane sulfonate saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, Examples thereof include alkenyl phosphate esters or salts thereof, and alkylsulfosuccinates.
  • amphoteric surfactant include a carboxyl type amphoteric surfactant and a sulfobetaine type amphoteric surfactant.
  • nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene higher alkyl ether; Polyoxyethylene alkyl aryl ethers such as oxyethylene nonylphenyl ether; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Such as tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate Lioxyethylene sorbitan fatty acid ester; sucrose fatty acid ester; polyoxyethylene sorbitol fatty acid ester such as polyoxyethylene sorbitol tetraoleate; polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol diste
  • the nonionic surfactant when a nonionic surfactant is used as the surfactant, the nonionic surfactant is preferably a polymer material, and the weight average molecular weight of the nonionic surfactant is 500 or more. It is preferable that By setting the weight average molecular weight of the nonionic surfactant to 500 or more, the positive electrode active material is effectively dispersed by the surfactant. This is presumably because the high molecular surfactant increases the affinity between the solvent and the surfactant and makes it easier to hold the solvent in the vicinity of the particles, thereby suppressing aggregation between the particles.
  • weight average molecular weight of the nonionic surfactant in the positive electrode mixture of the present invention is 1,000 to 50,000. By setting the weight average molecular weight within this range, the dispersibility of the positive electrode active material becomes better, and ions can be moved smoothly.
  • nonionic surfactants polyethylene glycol surfactants that have high ion conductivity and can be used for electrolytes of lithium ion batteries are preferred, polyethylene glycol fatty acid ester surfactants are more preferred, and polyethylene is more preferred. Glycolic stearates. Polyethylene glycol stearates have a high thickening effect and an excellent effect of preventing sedimentation and aggregation of the active material. Moreover, the movement of lithium ions in the surfactant can be promoted by using a polyethylene glycol-based surfactant for coating the active material.
  • a polyethyleneglycol type surfactant refers to what contains an ethylene glycol chain in an activator compound.
  • the surfactant used for the positive electrode mixture of the present invention preferably has an HLB of 13 to 20, more preferably 15 to 20, as measured by the Griffin method.
  • the HLB is more preferably 16-20.
  • HLB uses a surfactant in this range, the hydrophilic group and hydrophobic group of the surfactant are arranged in a well-balanced manner, so that uniform dispersion of the positive electrode active material and the binder resin having polarity in an aqueous solvent is promoted.
  • the compounding amount of the surfactant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. is there.
  • the solvent used in the positive electrode mixture of the present invention is not particularly limited as long as it is compatible with a surfactant that uniformly disperses the water-dispersible polymer binder resin and the positive electrode active material and inhibits sedimentation aggregation. Or an organic solvent.
  • water can be particularly preferably used as the solvent, but an organic solvent may be included as long as the above effects are not impaired.
  • organic solvent examples include cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; acetone, ethyl methyl ketone, disopropyl ketone, cyclohexanone, methylcyclohexane and ethyl.
  • cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane
  • aromatic hydrocarbons such as toluene, xylene and ethylbenzene
  • acetone ethyl methyl ketone
  • disopropyl ketone disopropyl ketone
  • cyclohexanone methylcyclohexane and ethyl.
  • Ketones such as cyclohexane; Chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; Esters such as ethyl acetate, butyl acetate, ⁇ -butyrolactone, and ⁇ -caprolactone; Acylonitriles such as acetonitrile and propionitrile Ethers such as tetrahydrofuran and ethylene glycol diethyl ether: alcohols such as methanol, ethanol, isopropanol, ethylene glycol and ethylene glycol monomethyl ether; Examples include amides such as loridone and N, N-dimethylformamide.
  • the positive electrode mixture of the present invention is only important to contain a positive electrode active material, a water-dispersible polymer binder resin, a conductive auxiliary agent, and a surfactant, and there is no particular limitation other than that,
  • additives may be included within a range that does not affect the battery reaction.
  • the positive electrode mixture of the present invention may contain components such as a reinforcing material, a thickener, a defoaming / leveling agent, and an electrolytic solution decomposition inhibitor in addition to the above components.
  • the reinforcing material various inorganic and organic spherical, plate, rod or fiber fillers may be used.
  • a reinforcing material By using a reinforcing material, a tougher and more flexible electrode can be obtained, and excellent long-term cycle characteristics can be imparted. These may be used alone or in combination of two or more.
  • the compounding amount of the reinforcing material is usually 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material. By setting the blending amount of the reinforcing material within the above range, high capacity and high load characteristics can be imparted.
  • the thickener is not particularly limited as long as it is a material that is stable with respect to the solvent and electrolyte used during electrode production and other materials used during battery use.
  • carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein and the like can be used. These may be used alone or in combination of two or more.
  • the compounding amount of the thickener is usually 0.01 to 20 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the positive electrode active material. By setting the blending amount of the thickener within the above range, it is possible to satisfactorily prevent sedimentation and aggregation of the positive electrode active material having a high specific gravity.
  • the defoaming / leveling agent As the defoaming / leveling agent, surfactants such as alkyl surfactants, silicone surfactants, fluorine surfactants, metal surfactants and the like can be used. By mixing the surfactant, it is possible to prevent the repelling that occurs during coating and to improve the smoothness of the electrode.
  • the blending amount of the defoaming / leveling agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. By making the compounding quantity of a defoaming and leveling agent into the said range, the coating malfunction at the time of electrode coating can be prevented, and productivity can be improved.
  • the electrolytic solution decomposition inhibitor vinylene carbonate or the like used in the electrolytic solution can be used.
  • the amount of the electrolytic solution decomposition inhibitor in the electrode is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the cycle characteristics and the high temperature characteristics can be further improved.
  • Other examples include nanoparticles such as fumed silica and fumed alumina. By mixing the nanoparticles, the thixotropy of the electrode forming mixture can be controlled.
  • the compounding amount of the nanoparticles in the positive electrode mixture of the present invention is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • the positive electrode mixture of the present invention is obtained by mixing the positive electrode active material, a water-dispersible polymer binder resin, a conductive additive, a surfactant and a solvent, and other additives as necessary. Can do.
  • the mixing method is not particularly limited, and for example, a method using a mixing apparatus such as a stirring type, a shaking type, and a rotary type can be employed. Further, a method using a dispersion kneader such as a homogenizer, a ball mill, a sand mill, a roll mill, and a planetary kneader may be employed.
  • the positive electrode of the present invention is obtained by applying the positive electrode mixture of the present invention to a current collector.
  • the positive electrode of the present invention is manufactured through an application step of applying the positive electrode mixture of the present invention on a current collector and a drying step of drying the obtained current collector to form a positive electrode mixture layer. be able to.
  • the positive electrode mixture layer may be formed on one side of the current collector, but is preferably formed on both sides.
  • the current collector used for the positive electrode of the present invention is not particularly limited as long as it is an electrically conductive and electrochemically durable material, but a metal material having heat resistance is preferable.
  • a metal material having heat resistance For example, iron, copper, aluminum, nickel, stainless steel, titanium, tantalum, gold, platinum, etc. can be mentioned.
  • aluminum or an aluminum alloy is preferable because of less oxidation deterioration during charging.
  • the shape of the current collector is not particularly limited, but a sheet having a thickness of about 5 to 100 ⁇ m can be preferably used.
  • the current collector is preferably used after roughening in advance in order to increase the adhesive strength with the positive electrode mixture layer.
  • the roughening method include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.
  • the mechanical polishing method it is possible to use abrasive cloth paper, abrasive wheels, emery buffs, wire brushes equipped with steel wires and the like to which abrasive particles are fixed.
  • an intermediate layer may be formed on the current collector surface in order to increase the adhesive strength and conductivity of the electrode layer.
  • ⁇ Application method> There is no limitation in particular also about the method of apply
  • the method of drying the current collector obtained by the above coating method is not particularly limited. For example, drying with warm air, hot air, low-humidity air, vacuum drying, or drying by irradiation with (far) infrared rays or electron beams. Can be mentioned.
  • the drying time is usually 5 to 30 minutes, and the drying temperature is usually 40 to 180 ° C.
  • ⁇ Rolling> In the production method of the present invention, it is preferable to go through a rolling process in which the porosity of the positive electrode mixture layer is lowered by pressure treatment using a die press, a roll press or the like after passing through a coating process and a drying process.
  • a preferable range of the porosity is 5% to 15%, and more preferably 7% to 13%. If the porosity exceeds 15%, the charging efficiency and the discharging efficiency are deteriorated, which is not preferable. On the other hand, when the porosity is less than 5%, it may be difficult to obtain a high volume capacity, or the positive electrode mixture layer may be easily peeled off from the current collector and may be defective.
  • curable resin as binder resin, it is preferable to have the process of hardening this curable resin.
  • the thickness of the positive electrode of the present invention is usually 5 to 400 ⁇ m, preferably 30 to 300 ⁇ m. By setting the thickness of the positive electrode within the above range, good flexibility and adhesion of the electrode plate can be obtained.
  • the nonaqueous electrolyte secondary battery of the present invention uses the positive electrode of the present invention, and has a positive electrode, a negative electrode, a separator, and an electrolytic solution.
  • the configuration of the nonaqueous electrolyte secondary battery of the present invention and the manufacturing method thereof will be described in detail.
  • the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is prepared by mixing a negative electrode active material, a conductive additive, a water-dispersible polymer binder resin, a solvent, and other additives as necessary to prepare a negative electrode mixture slurry. And it can manufacture by apply
  • any known material that has been conventionally used can be used as long as it is an active material that can occlude and release lithium ions.
  • Either a carbon-based active material or a non-carbon-based active material can be used. May be.
  • Examples of the carbon-based active material include graphite, soft carbon, and hard carbon.
  • non-carbon-based active material for example, known materials such as lithium metal, lithium alloy, oxide, sulfide, lithium-containing metal composite oxide can be used.
  • the conductive auxiliary agent and the solvent the conductive auxiliary agent and the solvent used in the production of the positive electrode of the present invention can be used.
  • binder resin what is generally used for nonaqueous electrolyte secondary batteries, such as SBR particle
  • the current collector used in the negative electrode for a non-aqueous electrolyte secondary battery according to the present invention is electrically conductive and electrochemically durable, like the positive electrode for a non-aqueous electrolyte secondary battery according to the present invention. If it is material, there will be no restriction
  • Electrolyte> Although there is no restriction
  • the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
  • LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation can be suitably used. These may be used alone or in combination of two or more.
  • the addition amount of the supporting electrolyte is usually 1% by mass or more, preferably 5% by mass or more, and usually 30% by mass or less, preferably 20% by mass or less, with respect to the electrolytic solution. If the amount of the supporting electrolyte is too small or too large, the ionic conductivity decreases, and the charging characteristics and discharging characteristics of the battery decrease.
  • the solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte, but dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate. (BC) and alkyl carbonates such as methyl ethyl carbonate (MEC); esters such as ⁇ -butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane; and tetrahydrofuran; including sulfolane and dimethyl sulfoxide Sulfur compounds can be used.
  • DMC dimethyl carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • alkyl carbonates such as methyl ethyl carbonate (MEC)
  • esters such as ⁇ -butyrolactone and methyl formate
  • ethers such as 1,2-dimethoxyethane
  • dimethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, and methyl ethyl carbonate are preferable because high ion conductivity is easily obtained and the use temperature range is wide. These may be used alone or in combination of two or more.
  • additives may be added to the electrolytic solution.
  • examples of the additive include carbonate compounds such as vinylene carbonate (VC), cyclohexylbenzene, diphenyl ether, and the like.
  • an electrolyte other than the above for the nonaqueous electrolyte secondary battery of the present invention
  • a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide or polyacrylonitrile with an electrolyte, lithium sulfide, LiI, Li 3
  • An inorganic solid electrolyte such as N can be used.
  • the separator is a porous substrate having pores, (a) a porous separator having pores, (b) a porous separator having a polymer coating layer formed on one or both sides, or (c) inorganic
  • a porous separator formed with a porous resin coating layer containing ceramic powder can be used, for example, polypropylene-based, polyethylene-based, polyolefin-based, aramid-based porous separator, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile ,
  • solid polymer electrolyte such as polyvinylidene fluoride hexafluoropropylene copolymer, polymer film for gel polymer electrolyte, separator coated with gelled polymer coat layer, inorganic filler, dispersion for inorganic filler
  • a porous membrane layer made of an agent It has been a separator, and the like can be given.
  • the negative electrode and the positive electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery and placed in the battery container, and the electrolytic solution is injected into the battery container and sealed.
  • an expanded metal, an overcurrent prevention element such as a fuse and a PTC element, a lead plate, etc. are inserted as necessary to prevent an increase in pressure inside the battery and overcharge / discharge. You can also.
  • the shape of the battery may be any shape such as a laminate cell type, a coin type, a button type, a sheet type, a cylindrical type, a square shape, and a flat type.
  • Example 1 Cell seed NMC-111 (LiNi 1/3 Co 1/3 Mn 1/3 O 2 ) manufactured by Nippon Kagaku Kogyo Co., Ltd., which is a ternary active material, is used as a positive electrode active material.
  • Adekabon titer HUX-822 polyurethane emulsion resin: solid content 40% by mass
  • ADEKA water-dispersible polymer binder resin with VGCF-H (vapor-grown carbon fiber) manufactured by Denko Corporation as a solid content ratio of 2% by mass. Solid content ratio 1.5% by mass, Kao Co., Ltd.
  • Emanon 3299RV polyethylene glycol distearate
  • water as a solvent is 60% by mass It mix
  • the produced positive electrode mixture was allowed to stand for 24 hours, and then applied to one side of an aluminum foil having a thickness of 20 ⁇ m using a 50 ⁇ m applicator. Then, it dried for 20 minutes at 150 degreeC with the hot-air circulation type box-type drying furnace, and removed the water which is a solvent. After cooling to room temperature, it is sandwiched between 1 mm stainless steel plates and rolled at room temperature for 1 minute at a pressure of 1.5 ton / cm 2 using a flat plate press to have an active material mixture layer of 80 ⁇ m on one side. A positive electrode plate was prepared.
  • Examples 2 to 9 Comparative Examples 1 and 2> Stirring and mixing in the same manner as in Example 1 except that the composition of the water-dispersible polymer binder resin, surfactant, thickener, conductive assistant, and positive electrode active material was changed as shown in Tables 1 to 4.
  • the positive electrode mixture was prepared, and the dispersibility and the stability of sedimentation aggregation were evaluated.
  • application, drying and rolling were performed in the same manner as in Example 1 to produce a positive electrode plate. The evaluation results are also shown in Tables 1 to 4.
  • the coating surface was cross-cut with a grid pattern of 25 squares with a cut interval of 2 mm according to JIS K-5600. The evaluation was made with “low” for those with little powder falling and “good” for those with no powder falling.
  • ⁇ Resistance value of electrode layer> The resistance value of the surface was measured using a tester (Mirium High Tester 3540, manufactured by Hioki Co., Ltd.) on the surface of the produced electrode plate.
  • Adekabon titer HUX-822 (polyurethane resin, molecular weight: 800,000 to 900,000) manufactured by ADEKA Corporation 2) HSV-900 (polyvinylidene fluoride resin) manufactured by Arkema Co., Ltd. 3) Movinyl LDM7523 (acrylic) / Silicone resin) Nippon Synthetic Chemical Co., Ltd. 4) Emanon 3299RV (polyethylene glycol distearate nonionic surfactant HLB: 19.2 Molecular weight: about 11200) Kao Corporation 5) Emanon 3199V (polyethylene) Glycol monostearate nonionic surfactant HLB: 19.4 molecular weight: about 6800) Kao Corp.
  • Emanon 1112 polyethylene glycol monolaurate nonionic surfactant HLB: 13.7 molecular weight: about 730
  • Adecamin 4MAC-30 cationic surfactant
  • Daicel CMC # 2200 manufactured by Daicel Finechem Corporation 9)
  • VGCF-H vapor-grown carbon fiber Showa Denko K.K.
  • SP-270 graphite powder
  • Cellseed NMC111 LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • LFP manufactured by Nippon Chemical Industry Co., Ltd.
  • NMP N-methylpyrrolidone
  • the positive electrode mixture of the present invention is excellent in the dispersibility of the positive electrode active material, the storage stability, and the coating property to the current collector.
  • the positive electrode produced using the positive electrode mixture is a positive electrode mixture layer. It can be seen that it has excellent adhesion to the current collector.
  • the comparative example seemed to be well dispersed in the slurry state, but rough particulate lumps and the like remained, the dispersibility was poor, and coating film formation was difficult.

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  • Electrochemistry (AREA)
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Abstract

L'invention fournit un mélange d'électrode positive aqueux, une électrode positive et une batterie secondaire à électrolyte non aqueux mettant en œuvre celle-ci. Lequel mélange d'électrode positive permet d'obtenir une électrode positive se révélant excellente en termes de propriétés de dispersion d'une matière active d'électrode positive, de stabilité de conservation et de propriétés de revêtement lorsqu'un collecteur est revêtu, et présentant en outre une excellente adhérence du collecteur et de la matière active d'électrode positive après revêtement du collecteur. Plus précisément, le mélange d'électrode positive comprend la matière active d'électrode positive, une résine de liant polymère hydrodispersable, un agent auxiliaire conducteur et un agent tensio-actif.
PCT/JP2012/081151 2011-12-26 2012-11-30 Mélange d'électrode positive, électrode positive, et batterie secondaire à électrolyte non aqueux mettant en œuvre celle-ci WO2013099520A1 (fr)

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CN201280064831.4A CN104025350A (zh) 2011-12-26 2012-11-30 正极合剂、正极、以及使用其的非水电解质二次电池
JP2013551551A JP6055782B2 (ja) 2011-12-26 2012-11-30 正極合剤、正極、およびそれを用いた非水電解質二次電池

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JP2017183241A (ja) * 2016-03-31 2017-10-05 積水化学工業株式会社 蓄電デバイス電極用バインダー
CN106099099A (zh) * 2016-08-26 2016-11-09 新乡天力锂能股份有限公司 一种镍钴锰酸锂薄膜材料的制备方法
US11824189B2 (en) 2018-01-09 2023-11-21 South Dakota Board Of Regents Layered high capacity electrodes
JP6856812B1 (ja) * 2020-10-21 2021-04-14 第一工業製薬株式会社 電極用結着剤組成物、電極用塗工液組成物、蓄電デバイス用電極及び蓄電デバイス
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