WO2012036288A1 - 非水二次電池などの集電積層体の導電性保護層形成用ペースト - Google Patents
非水二次電池などの集電積層体の導電性保護層形成用ペースト Download PDFInfo
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- WO2012036288A1 WO2012036288A1 PCT/JP2011/071265 JP2011071265W WO2012036288A1 WO 2012036288 A1 WO2012036288 A1 WO 2012036288A1 JP 2011071265 W JP2011071265 W JP 2011071265W WO 2012036288 A1 WO2012036288 A1 WO 2012036288A1
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a paste for forming a conductive protective layer of a current collecting laminate such as a non-aqueous secondary battery such as a lithium secondary battery or an electric double layer capacitor, a current collecting laminate, an electrode laminate, and a lithium secondary battery. And a non-aqueous secondary battery such as an electric double layer capacitor.
- the lithium secondary battery includes a positive electrode in which a positive electrode mixture layer containing a positive electrode active material such as a lithium-containing composite oxide is provided on a positive electrode current collector such as an aluminum foil, and a negative electrode current collector such as an aluminum foil.
- Patent Document 1 proposes forming a surface protective layer containing a heterocyclic compound on the current collector.
- Patent Document 2 in order to prevent the corrosion of the positive electrode current collector (aluminum foil) by the lithium imide salt that is an electrolyte salt on the current collector, noble metals, alloys, conductive ceramics, semiconductors, organic semiconductors and It has been proposed to form a protective layer containing at least one material selected from conductive polymers.
- the conductive polymer include polyaniline, polypyrrole, polyacene, polydisulfide, and polyparaphenylene.
- a mixed solution in which a conductive polymer, a binder, and dopan (aromatic sulfonic acid ester) are dissolved in a solvent is cast or applied, and then heated and dried. Illustrated.
- Patent Document 3 describes that a conductive adhesive film is formed by spray-coating a slurry containing carbon black on a current collector (paragraph [0039]).
- Patent Document 4 proposes using an epoxy resin as a binder for the paste for forming the current collector protective layer.
- a method of winding an electrode (winding type or spiral type) is mainly used, and thus high flexibility is required for the electrode.
- the surface protective layer of the heterocyclic compound described in Patent Document 1 is insufficient in terms of oxidation potential, and the material described in Patent Document 2 is hard and lacks flexibility.
- it is effective in preventing the lithium imide salt from corroding the aluminum foil, but is insufficient when used at a high voltage.
- Patent Document 3 describes that carbon black is blended, but there is no description about the binder.
- the epoxy resin used as a binder in Patent Document 4 has a low withstand voltage, and is difficult to use for specifications (uses) that require high voltage as described above.
- the present invention provides a conductive layer forming paste for a current collector laminate that can protect the current collector from corrosion without damaging the battery characteristics even in high voltage specifications, a current collector laminate having the conductive layer, an electrode, and a lithium secondary battery. It aims at providing nonaqueous secondary batteries, such as a secondary battery and an electric double layer capacitor.
- the present invention relates to a conductive protective layer forming paste for protecting a current collector comprising polytetrafluoroethylene and a conductive filler (b).
- the conductive protective layer forming paste of the present invention also contains a solvent in addition to polytetrafluoroethylene and the conductive filler (b) (hereinafter referred to as “conductive protective layer forming paste (I)”). ). ) Is preferable.
- the conductive filler (b) is preferably contained in an amount of 5 to 1000 parts by mass with respect to 100 parts by mass of PTFE.
- the conductive protective layer forming paste of the present invention is also referred to as a polytetrafluoroethylene aqueous dispersion (a) and a conductive filler (b) (hereinafter referred to as “conductive protective layer forming paste (II)”). . ) Is preferable.
- the conductive filler (b) is preferably contained in an amount of 5 to 1000 parts by mass with respect to 100 parts by mass of the PTFE particles in the PTFE dispersion (a).
- the conductive protective layer forming paste further includes tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyamideimide (PAI), polyimide (PI), polyvinylidene fluoride (PVdF), and tetrafluoro as a binder. It may contain at least one polymer selected from the group consisting of ethylene-vinylidene fluoride copolymers.
- the conductive filler (b) may be a particulate filler, a fibrous filler, or a combination thereof. Preferably, it is a conductive carbon filler.
- the present invention also relates to a current collecting laminate in which a conductive protective layer (A) obtained by applying the conductive protective layer forming paste of the present invention is provided on a current collector (B).
- the volume resistivity of the conductive protective layer (A) is preferably 0.001 to 50 ⁇ ⁇ cm.
- the present invention further relates to an electrode laminate in which an electrode mixture layer (C) is provided on the conductive protective layer (A) of the current collector laminate of the present invention.
- the present invention also includes a non-aqueous secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein at least one of the positive electrode and the negative electrode is the electrode laminate of the present invention, particularly a lithium secondary battery or an electric double layer capacitor.
- a non-aqueous secondary battery comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein at least one of the positive electrode and the negative electrode is the electrode laminate of the present invention, particularly a lithium secondary battery or an electric double layer capacitor.
- a current collector laminate, an electrode laminate, and a lithium secondary battery capable of protecting the current collector from corrosion without impairing battery characteristics even in high voltage specifications. be able to.
- FIG. 2 is a chart showing the results of oxidation potential (CV) measurement of the current collecting laminate of the present invention produced in Example 1.
- FIG. 2 is a chart showing the results of oxidation potential (CV) measurement of the current collecting laminate of the present invention produced in Example 1.
- the conductive protective layer forming paste of the present invention contains PTFE and a conductive filler (b), thereby protecting the current collector from corrosion without impairing battery characteristics even in a high voltage specification. Moreover, the protective layer obtained from the conductive protective layer forming paste is advantageous in that it does not impair the flexibility of the electrode.
- PTFE may be a homopolymer of TFE or modified PTFE modified with other monomers such as a very small amount of hexafluoropropylene (HFP) or perfluoro (alkyl vinyl ether) (PAVE).
- the molecular weight may be a high molecular weight that can be fiberized, and is, for example, about 1 to 5 million.
- Modified PTFE is a polymer having less than 1 mol% of polymerized units based on other monomers.
- PTFE is preferably PTFE particles obtained from an aqueous PTFE dispersion.
- examples of such an aqueous PTFE dispersion include the PTFE aqueous dispersion (a) described later.
- the average primary particle diameter of the PTFE particles is preferably 0.1 to 0.5 ⁇ m.
- the average primary particle diameter is a value measured by a light laser scattering method.
- the conductive protective layer forming paste of the present invention may contain other resin as a binder in addition to PTFE.
- resins include tetrafluoroethylene (TFE) -hexafluoropropylene (HFP) copolymer (FEP), polyamideimide (PAI), polyimide (PI), polyvinylidene fluoride (PVdF), and tetrafluoroethylene (TFE).
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- PAI polyamideimide
- PI polyimide
- PVdF polyvinylidene fluoride
- TFE tetrafluoroethylene
- At least one polymer selected from the group consisting of TFE-HFP copolymer (FEP) and TFE-VdF copolymer is more preferable.
- the FEP and TFE-VdF copolymer is a copolymer having a polymer unit based on a monomer other than TFE of 1 mol% or more.
- the ratio of the other resin is 300 parts by mass or less, further 200 parts by mass or less with respect to 100 parts by mass of PTFE (solid content), and the lower limit is preferably about 10 parts by mass.
- non-fluorinated rubber may be used in combination.
- the conductive filler (b) used in the present invention is a filler having a volume resistivity of 1 ⁇ 10 ⁇ 9 to 1 ⁇ ⁇ cm.
- the preferred volume resistivity is 1 ⁇ 10 ⁇ 8 to 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm.
- the conductive filler (b) may be a particulate filler, a fibrous filler, or a combination thereof.
- a conductive carbon filler is preferable.
- the particulate conductive carbon filler examples include ketjen black, acetylene black, nanoporous carbon, graphite (natural graphite, artificial graphite), furnace black, channel black, etc. Among them, chemical resistance and conductivity are good. From the viewpoint of good fluidity of the composition, at least one selected from the group consisting of nanoporous carbon and graphite is preferable, and from the viewpoint of good chemical resistance and conductivity, ketjen black and acetylene black At least one selected from the group consisting of The average particle size is preferably 0.02 to 50 nm, and more preferably 0.025 to 40 nm from the viewpoint of good conductivity. The average particle diameter of the carbon filler can be measured by a light laser scattering method after being dispersed in an organic solvent.
- fibrous conductive carbon filler examples include carbon fibers, carbon nanotubes, and carbon nanofibers.
- at least one selected from the group consisting of carbon nanotubes and carbon nanofibers is preferable from the viewpoint of good conductivity.
- Species are preferred, and carbon fibers, particularly carbon fibers produced by a gas phase method, are preferred from the viewpoint of good cost performance.
- Fibrous carbon preferably has an average fiber diameter of 0.1 to 200 nm, more preferably 1 to 200 nm, from the viewpoint of good conductivity. Moreover, it is also preferable that it is 50 nm or less. Further, the ratio of average fiber length / average fiber diameter is preferably 5 or more, and more preferably 10 or more from the viewpoint of good conductivity. Moreover, it is preferable from a point with easy preparation of a composition that it is 1000 or less and also 500 or less.
- the conductive filler (b) is preferably a filler that is at least one selected from the group consisting of ketjen black, acetylene black, nanoporous carbon, graphite, carbon fiber, carbon nanotube, and carbon nanofiber.
- the particulate carbon filler and the fibrous carbon filler may be used in combination. When used in combination, for example, it becomes easier to control the aspect ratio of the conductivity of the protective film, which will be described later, and the conductivity of the protective film is further improved than when it is used alone.
- the mixing ratio (mass ratio) of the particulate carbon filler / fibrous carbon filler is preferably 10/90 or more, and more preferably 20/80 or more from the viewpoint of giving good fluidity to the composition. Further, it is preferably 90/10 or less, and more preferably 80/20 or less from the viewpoint of easy control of the conductive aspect ratio in the protective film.
- the amount of the conductive filler (b) is preferably 5 to 1000 parts by mass with respect to 100 parts by mass of PTFE.
- the amount is less than 5 parts by mass, the conductivity of the protective film may be insufficient, which is not preferable.
- it exceeds 1000 mass parts preparation of a composition may become difficult and it is not preferable.
- the more preferable upper limit is 500 parts by mass, more preferably 300 parts by mass, and particularly preferably 200 parts by mass from the viewpoint of good stability during molding.
- Preparation of a conductive protective layer forming paste 100 parts by mass is the most preferable from the viewpoint of ease.
- a conductive carbon filler and a metal filler may be used in combination.
- the total of the conductive filler (b) and the metal filler is preferably 5 to 1000 parts by mass with respect to 100 parts by mass of PTFE.
- the upper limit is more preferably 500 parts by mass, still more preferably 300 parts by mass, particularly preferably 200 parts by mass, and most preferably 100 parts by mass.
- the combination of the conductive carbon filler and the metal filler include a combination of a particulate carbon filler and a particulate and / or fibrous metal filler, a fibrous carbon filler and a particulate and / or fibrous metal filler. And is appropriately selected according to the required performance.
- the mixing ratio may be appropriately selected in consideration of the degree and weight of conductivity of each filler, the elasticity and flexibility of the generated conductive layer, and the like.
- a non-conductive (volume resistivity exceeds 1 ⁇ ⁇ cm) filler may be used in combination.
- the nonconductive filler include a nonconductive carbon filler, a nonconductive inorganic oxide filler, and a nonconductive resin filler. Specifically non-conductive carbon black, non-conductive Austin black, non-conductive graphite (natural graphite, artificial graphite), non-conductive carbon nanotube, non-conductive graphitized carbon black, etc.
- Carbon filler non-conductive such as silica, silicate, clay, diatomaceous earth, montmorillonite, talc, calcium carbonate, calcium silicate, barium sulfate, fatty acid calcium, titanium oxide, bengara, boron nitride, aluminum nitride, magnesium oxide, alumina
- Inorganic oxide filler polyethylene, heat-resistant engineering plastics, PTFE-based tetrafluoroethylene-ethylene-ethylene-tetrafluoroethylene copolymer (ETFE), fluorocarbons such as polyvinylidene fluoride (PVdF) Rimmer, such as a non-conductive resin filler such as polyimide and the like.
- the blending amount may be appropriately selected in consideration of the effect of blending and the degree and weight of conductivity of the conductive filler (b), the elasticity and flexibility of the generated conductive layer, and the like.
- a processing aid and an adhesive that cures by crosslinking are further used unless the object of the present invention is impaired. May be.
- the conductive protective layer forming paste of the present invention is preferably a conductive protective layer forming paste (I) containing a solvent in addition to polytetrafluoroethylene and the conductive filler (b).
- the solvent is usually water, an organic solvent, or a mixed solvent of water and an organic solvent.
- the solvent is preferably water or a mixed solvent of water and an organic solvent, and more preferably water.
- the solvent is preferably an organic solvent or a mixed solvent of water and an organic solvent, and more preferably an organic solvent.
- the amount of the solvent may be an amount that provides an appropriate concentration for coating.
- organic solvents examples include ketones such as methyl ethyl ketone, acetone, cyclohexanone, dibutyl ketone, and methyl isobutyl ketone; amides such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide; butyl acetate, amyl acetate, butyl propionate, and ethyl cellosolve And esters such as methyl cellosolve; polar solvents such as ethers such as tetrahydrofuran, diglyme and triglyme; and aromatic solvents such as toluene and xylene. Alcohols may be used in combination.
- ketones such as methyl ethyl ketone, acetone, cyclohexanone, dibutyl ketone, and methyl isobutyl ketone
- amides such as N-methylpyrrolidone, dimethylacetamide, and dimethylformamide
- the conductive protective layer-forming paste of the present invention is also one of the preferred forms that is a conductive protective layer-forming paste (II) containing a polytetrafluoroethylene aqueous dispersion (a) and a conductive filler (b). It is.
- the conductive protective layer forming paste (II) of the present invention is prepared by adding a conductive filler (b) to a PTFE aqueous dispersion (a).
- the solvent is water.
- an organic solvent may be added from the viewpoint of improving applicability. Examples of the organic solvent include those exemplified for the conductive protective layer forming paste (I).
- ketones such as methyl ethyl ketone, acetone, cyclohexanone, dibutyl ketone, methyl isobutyl ketone; amides such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide; butyl acetate, amyl acetate, butyl propionate, ethyl cellosolve, methyl cellosolve, etc.
- Esters polar solvents such as ethers such as tetrahydrofuran, diglyme and triglyme, and aromatic solvents such as toluene and xylene. Alcohols may be used in combination.
- the conductive filler (b) is preferably contained in an amount of 5 to 1000 parts by mass with respect to 100 parts by mass of the polytetrafluoroethylene (solid content) in the polytetrafluoroethylene dispersion (a).
- the upper limit is more preferably 500 parts by mass, still more preferably 300 parts by mass, particularly preferably 200 parts by mass, and most preferably 100 parts by mass.
- the PTFE aqueous dispersion (a) is preferably a PTFE aqueous dispersion (dispersion) obtained by emulsion polymerization.
- the PTFE particles in the aqueous dispersion are preferably dispersed as primary particles (average particle size is 0.1 to 0.5 ⁇ m).
- the solid content (PTFE particles) concentration of the PTFE aqueous dispersion is preferably about 1 to 80% by mass, more preferably about 10 to 70% by mass from the viewpoint of good stability of the aqueous dispersion.
- Preparation of the conductive protective layer forming paste of the present invention may be performed by mixing the components by a normal mixing method.
- the conductive protective layer forming paste of the present invention can be prepared by adding the conductive filler (b) to the PTFE aqueous dispersion (a).
- the solvent is water or a mixed solvent of water and an organic solvent.
- the PTFE aqueous dispersion (a) may be phase-shifted into an organic solvent to form an organosol, and then the conductive filler (b) may be added.
- the solvent is an organic solvent or a mixed solvent of water and an organic solvent.
- the conductive protective layer (A) in the present invention is formed by applying the conductive protective layer forming paste of the present invention to the current collector (B) to constitute a current collector laminate.
- the conductive protective layer (A) formed from the conductive protective layer-forming paste of the present invention is provided to protect the current collector, and includes a current collector and an electrode mixture layer (C). A layer provided between them is preferable.
- the blending ratio of PTFE and the conductive filler (b) is the ratio described in the conductive protective layer forming paste.
- the blending ratio of components other than PTFE and the conductive filler (b) is also the same as that of the conductive protective layer forming paste.
- the method for forming the conductive protective layer (A) may be a conventionally known method. For example, apply to the current collector by roller coating, brush coating, dip coating, spray coating, gravure coating, coil coating, curtain flow coating, etc., and let it dry naturally or heat at ambient temperature To form a protective layer.
- the conductive protective layer (A) thus obtained can control the volume resistivity in the range of 0.001 to 50 ⁇ ⁇ cm, and if necessary, 0.001 to 10 ⁇ ⁇ cm, further 1 ⁇ ⁇ cm or less.
- a highly conductive protective layer can be provided.
- the thickness of the conductive protective layer (A) may be appropriately selected within the range of 0.5 to 50 ⁇ m. For example, from the viewpoint of reducing the resistance, it is 0.5 ⁇ m or more, more preferably 1.0 ⁇ m or more. From the point of preparation, 50 micrometers or less, Furthermore, 10 micrometers or less are preferable.
- the present invention is particularly effective for a material that is corroded by a lithium salt in an electrolytic solution.
- the material constituting the current collector (B) include aluminum or an alloy thereof, stainless steel, nickel or an alloy thereof, titanium or an alloy thereof, and aluminum or stainless steel having a surface treated with carbon or titanium. Used. Among these, aluminum or an aluminum alloy is mentioned as a current collector (B) that is particularly protected. These materials can also be used after oxidizing the surface. Moreover, since adhesiveness goes up by making an unevenness
- the thickness of the current collector (B) is usually in the range of 5 to 30 ⁇ m.
- the current collecting laminate of the present invention may be used for the positive electrode or the negative electrode.
- a great effect is exhibited when used for a positive electrode in which the current collector is severely corroded.
- the present invention also relates to an electrode laminate in which an electrode mixture layer (C) is provided on the conductive protective layer (A) of the current collector laminate of the present invention.
- the electrode mixture forming the electrode mixture layer (C) contains an electrode active material and a binder, and if necessary, is prepared by blending other materials.
- a conventionally known positive electrode mixture and negative electrode mixture can be used, but this is particularly effective in the case of an electrode mixture having a high voltage specification.
- a lithium-containing transition metal composite oxide that produces a high voltage is particularly preferable.
- the formula (1) Li a Mn 2-b M 1 b O 4 (where 0.9 ⁇ a; 0 ⁇ b ⁇ 1.5; M 1 is selected from the group consisting of Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and Ge
- Ni nickel composite oxide, or the formula (3): LiCo 1-d M 3 d 2 (where, 0 ⁇ d ⁇ 0.5; M 3 is Fe, Ni, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si and A lithium-cobalt composite oxide represented by (at least one metal selected from the group consisting of Ge) is preferable.
- LiCoO 2 , LiMnO 2 , LiNiO 2 , LiMn 2 O 4 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , or LiNi 1/3 Co 1/3 Mn 1/3 O 2 is preferable from the viewpoint of providing a lithium secondary battery having high energy density and high output.
- positive electrode actives such as LiFePO 4 , LiNi 0.8 Co 0.2 O 2 , Li 1.2 Fe 0.4 Mn 0.4 O 2 , LiNi 0.5 Mn 0.5 O 2 , LiV 3 O 6, etc. It may be a substance.
- the compounding amount of the positive electrode active material is preferably 50 to 99% by mass, more preferably 80 to 99% by mass of the positive electrode mixture, from the viewpoint of high battery capacity.
- Examples of the negative electrode active material include carbon materials, and also include metal oxides and metal nitrides capable of inserting lithium ions.
- Examples of carbon materials include natural graphite, artificial graphite, pyrolytic carbons, cokes, mesocarbon microbeads, carbon fibers, activated carbon, and pitch-coated graphite.
- Metal oxides capable of inserting lithium ions include tin and Examples of the metal compound containing silicon and titanium include tin oxide, silicon oxide, and lithium titanate. Examples of the metal nitride include Li 2.6 Co 0.4 N.
- the compounding amount of the negative electrode active material is preferably 50 to 99% by mass, more preferably 80 to 99% by mass of the negative electrode mixture, from the viewpoint of high battery capacity.
- binder examples include fluorine resin, non-fluorine resin, and rubber.
- the fluororesin is preferably at least one polymer selected from the group consisting of PTFE and PVdF.
- PTFE may be a homopolymer of tetrafluoroethylene, or modified PTFE in which a small amount of other monomers such as hexafluoropropylene (HFP) and perfluoro (alkyl vinyl ether) (PAVE) are copolymerized. Also good.
- HFP hexafluoropropylene
- PAVE perfluoro (alkyl vinyl ether)
- non-fluorinated resins examples include polyacrylic acid.
- rubber examples include ethylene-propylene / diene copolymer rubber (EPDM) and styrene-butadiene copolymer rubber (SBR).
- the blending amount of the binder is preferably 0.5 to 15% by mass, more preferably 0.5 to 10% by mass of the electrode mixture from the viewpoint of high battery capacity.
- Other components include fluorine resins such as TFE-HFP copolymer resins, ETFE and VdF copolymer resins for improving the adhesion of electrode mixtures and for improving the utilization of active materials; Fluororubber and acrylic rubber for improving; Cellulosic resin such as cellulose acetate for improving withstand voltage; Additives used for manufacturing electrodes of lithium secondary batteries, for example, conductive materials and thickeners for electrode preparation , Other polymers, surfactants and the like.
- the conductive material include conductive carbon black such as acetylene black and ketjen black; and carbonaceous materials such as graphite and carbon fiber.
- the electrode mixture layer (C) is appropriately mixed using an appropriate solvent to prepare an electrode mixture forming composition as a uniform mixture, and the conductivity of the current collecting laminate. It can carry out by methods, such as a spin coat, a blade coat, a roll coat, and a dip coat, on a protective layer (A).
- the electrode that has been subjected to the drying treatment is usually further subjected to a rolling treatment if necessary, followed by a cutting treatment, and is processed into a predetermined thickness and dimensions to obtain an electrode for a lithium secondary battery.
- the rolling process and the cutting process may be ordinary methods.
- the current collector is protected from the lithium salt in the electrolytic solution by the protective layer using PTFE as the binder, corrosion of the current collector can be suppressed even at a high operating voltage, and cycle characteristics Degradation of battery characteristics such as can be suppressed.
- the present invention also relates to a non-aqueous secondary battery, particularly a lithium secondary battery.
- the lithium secondary battery of the present invention includes a positive electrode, a negative electrode, and a non-aqueous electrolyte, and uses the electrode laminate of the present invention as the positive electrode and / or the negative electrode.
- electrodes other than the electrode of this invention for one of a positive electrode or a negative electrode
- a conventionally well-known electrode can be used for those positive electrodes or negative electrodes.
- the non-aqueous electrolyte is not particularly limited as long as it is an electrolyte containing an electrolyte salt and an organic solvent for dissolving the electrolyte salt and is used in a lithium secondary battery.
- Examples of the electrolyte include known electrolyte salts such as LiPF 6 , LiBF 4 , LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 C 2 F 5 ) 2.
- Examples of the organic solvent include ethylene carbonate and dimethyl Hydrocarbon solvents such as carbonate, methyl ethyl carbonate, diethyl carbonate, propylene carbonate; fluorine solvents such as HCF 2 CF 2 CH 2 OCF 2 CF 2 H, CF 3 COOCF 3 , CF 3 COOCH 2 CF 3 , and mixtures thereof Although a solvent etc. can be illustrated, it is not limited only to these.
- a separator may be disposed in the lithium secondary battery of the present invention.
- the separator is not particularly limited, and is a microporous polyethylene film, a microporous polypropylene film, a microporous ethylene-propylene copolymer film, a microporous polypropylene / polyethylene bilayer film, or a microporous polypropylene / polyethylene / polypropylene trilayer film.
- a film in which an aramid resin is coated on a separator made for the purpose of improving safety such as a short circuit caused by Li dentlite, or a film in which a resin containing polyamideimide and an alumina filler is coated on a separator is also included (for example, (See JP 2007-299612 A and JP 2007-324073 A).
- the lithium secondary battery of the present invention is useful as a large-sized lithium secondary battery for a hybrid vehicle or a distributed power source, a small-sized lithium secondary battery such as a mobile phone or a portable information terminal.
- the present invention also relates to an electric double layer capacitor using the electrode of the present invention.
- the basic structure of the electric double layer capacitor is the same as the conventional one except that the electrode of the present invention is used as the electrode.
- the measurement method and evaluation method employed in the present invention are as follows.
- volume resistivity is measured by the 4-terminal method.
- a BAS voltammetric closed cell (VC-4) place the CV electrode prepared above on the working electrode, use Li for the counter electrode and reference electrode, and put 3 ml of the above electrolyte into the measuring cell. Make it.
- the produced cell is scanned at 5 mV / sec from 3 V to 5.3 V at 25 ° C. (constant) using a potentio-galvanostat (Solartron type 1287), and the current change is measured.
- Example 1 PTFE aqueous dispersion (D210C manufactured by Daikin Industries, Ltd.) (a) was adjusted to a solid content concentration of 20% by mass with 100 g of PTFE aqueous dispersion, and acetylene black (average particle size 35 nm) as a conductive filler (b) was added. 50 g and 2 g of acrylic resin (A10H) as a thickener were added to prepare a conductive protective layer forming paste. Next, this paste was uniformly applied on the positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) to form a conductive fluorine-containing resin layer (thickness of 5 ⁇ m) on one surface, and heated at 80 ° C.
- the oxidation potential (CV) of the obtained positive electrode current collector laminate was measured. The results are shown in FIG.
- Example 1 in which the conductive protective layer is formed, the reference voltage is 5.3 V. There is no big peak. This shows that the aluminum foil is not oxidized by forming a conductive protective layer.
- Example 2 PTFE aqueous dispersion (D210C manufactured by Daikin Industries, Ltd.) (a) and FEP aqueous dispersion (ND110 manufactured by Daikin Industries, Ltd.) were mixed at a solid content ratio (mass ratio) of 6/4, and then the solid content concentration 100 g of an aqueous dispersion adjusted to 20% by mass was prepared.
- a conductive protective layer forming paste was prepared by adding 50 g of acetylene black (average particle size 35 nm) as the conductive filler (b) and 1 g of carboxymethyl cellulose (CMC) as the thickener.
- this paste was uniformly applied on the positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) to form a conductive fluorine-containing resin layer (thickness of 5 ⁇ m) on one surface, and heated at 80 ° C. with a hot air dryer at 10 ° C. Dried for minutes. Also, apply the paste prepared in the same way on the opposite (back) side and dry it, then press to form a conductive fluorine-containing resin layer (total thickness: 10 ⁇ m) on both sides. And then dried at 250 ° C. for 10 hours to produce a positive electrode current collector laminate having a conductive protective layer formed on both sides. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 3 PTFE aqueous dispersion (D210C manufactured by Daikin Industries, Ltd.) (a) and FEP aqueous dispersion (ND110 manufactured by Daikin Industries, Ltd.) were mixed at a solid content ratio (mass ratio) of 6/4, followed by methyl isobutyl. 100 g of an organosol which was phase-inverted to ketone (MIBK) and further adjusted to a solid content concentration of 20% by mass was prepared. 50 g of acetylene black (average particle size 35 nm) as the conductive filler (b) was added thereto to prepare a conductive protective layer forming paste.
- MIBK phase-inverted to ketone
- this paste was uniformly applied on the positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) to form a conductive fluorine-containing resin layer (thickness of 5 ⁇ m) on one surface, and heated at 80 ° C. with a hot air dryer at 10 ° C. Dried for minutes. Also, apply the paste prepared in the same way on the opposite (back) side and dry it, then press to form a conductive fluorine-containing resin layer (total thickness: 10 ⁇ m) on both sides. And then dried at 250 ° C. for 10 hours to produce a positive electrode current collector laminate having a conductive protective layer formed on both sides. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 4 In Example 2, a paste for forming a conductive protective layer was prepared in the same manner except that ketjen black was used instead of acetylene black, and a positive electrode current collector (15 ⁇ m thick aluminum) was prepared in the same manner as in Example 2.
- the positive electrode current-collecting laminated body in which the electroconductive protective layer was formed in both surfaces was produced.
- the volume resistivity was measured. The results are shown in Table 1.
- Example 5 In Example 2, a vapor-grown carbon fiber (average fiber length: 15 ⁇ m, average fiber diameter: 150 nm, VGCF (registered trademark) manufactured by Showa Denko KK) was used in the same manner in place of acetylene black. A paste for forming a conductive protective layer was prepared, applied to a positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) and dried in the same manner as in Example 2, and a positive current collector laminated layer having a conductive protective layer formed on both sides The body was made. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 6 In Example 2, a paste for forming a conductive protective layer was prepared in the same manner except that the amount of acetylene black was changed to 150 g. A positive electrode current collector (a 15 ⁇ m thick aluminum foil) was prepared in the same manner as in Example 2. ) And dried to produce a positive electrode current collector laminate having conductive protective layers formed on both sides. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 7 In Example 2, a paste for forming a conductive protective layer was prepared in the same manner except that the amount of acetylene black was changed to 2.5 g, and a positive electrode current collector (thickness of 15 ⁇ m) was prepared in the same manner as in Example 2. The positive electrode current-collecting laminated body in which the electroconductive protective layer was formed in both surfaces was produced. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 8 PTFE aqueous dispersion (D210C manufactured by Daikin Industries, Ltd.) (a) and P (TFE-VDF) [TFE-VdF copolymer] aqueous dispersion (VT470 manufactured by Daikin Industries, Ltd.) ), And then phase-inverted to methyl isobutyl ketone (MIBK) to prepare 100 g of an organosol adjusted to a solid content concentration of 20% by mass. 50 g of acetylene black (average particle size 35 nm) as the conductive filler (b) was added thereto to prepare a conductive protective layer forming paste.
- MIBK phase-inverted to methyl isobutyl ketone
- this paste was uniformly applied on the positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) to form a conductive fluorine-containing resin layer (thickness of 5 ⁇ m) on one surface, and heated at 80 ° C. with a hot air dryer at 10 ° C. Dried for minutes. Also, apply the paste prepared in the same way on the opposite (back) side and dry it, then press to form a conductive fluorine-containing resin layer (total thickness: 10 ⁇ m) on both sides. And then dried at 250 ° C. for 10 hours to produce a positive electrode current collector laminate having a conductive protective layer formed on both sides. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 9 PTFE aqueous dispersion (D210C manufactured by Daikin Industries, Ltd.) (a) and P (TFE-VDF) aqueous dispersion (VT470 manufactured by Daikin Industries, Ltd.) were mixed at a solid content ratio (mass ratio) of 8/2. Subsequently, 100 g of an organosol which was phase-inverted to N-methylpyrrolidone (NMP) and further adjusted to a solid content concentration of 20% by mass was prepared. 50 g of acetylene black (average particle size 35 nm) as the conductive filler (b) was added thereto to prepare a conductive protective layer forming paste.
- NMP N-methylpyrrolidone
- this paste was uniformly applied on the positive electrode current collector (aluminum foil having a thickness of 15 ⁇ m) to form a conductive fluorine-containing resin layer (thickness of 5 ⁇ m) on one surface, and heated at 80 ° C. with a hot air dryer at 10 ° C. Dried for minutes. Also, apply the paste prepared in the same way on the opposite (back) side and dry it, then press to form a conductive fluorine-containing resin layer (total thickness: 10 ⁇ m) on both sides. And then dried at 250 ° C. for 10 hours to produce a positive electrode current collector laminate having a conductive protective layer formed on both sides. About the obtained positive electrode current collection laminated body, the volume resistivity was measured. The results are shown in Table 1.
- Example 10 LiNi 1/3 Mn 1/3 Co 1/3 O 2 , carbon black and polyvinylidene fluoride (manufactured by Kureha Chemical Co., Ltd., trade name KF-1000) on the positive electrode current-collecting laminate of the present invention produced in Example 1 ) was mixed in 90/3/7 (mass% ratio) in N-methyl-2-pyrrolidone to uniformly apply a positive electrode mixture slurry in the form of a slurry, and dried to form a positive electrode mixture A layer (thickness 50 ⁇ m) was formed, and then compression molded by a roller press to produce a positive electrode laminate.
- KF-1000 polyvinylidene fluoride
- the positive electrode laminate is punched into a diameter of 1.6 mm with a punching machine to produce a circular positive electrode.
- styrene-butadiene rubber dispersed in distilled water is added to artificial graphite powder (manufactured by Hitachi Chemical Co., Ltd., trade name: MAG-D) to a solid content of 6% by mass and mixed with a disperser.
- the slurry is uniformly coated on a negative electrode current collector (copper foil having a thickness of 10 ⁇ m), dried, and a negative electrode mixture layer is formed.
- a circular negative electrode is produced by punching to a size of 1.6 mm.
- the electrolyte is added to a concentration of 0.0 mol / liter), and after the electrolyte has sufficiently penetrated into the separator, etc., it is sealed, precharged and aged, and a coin-type lithium secondary battery is obtained. Make it.
- Charging / discharging conditions Charging: Holds until the charging current becomes 1 / 10C at 1.0C, 4.7V (CC / CV charging) Discharge: 1C 3.0Vcut (CC discharge)
- Cycle retention rate (%) 100 cycle discharge capacity (mAh) / 5 cycle discharge capacity (mAh) ⁇ 100
- Example 11 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that the positive electrode current collector in Example 2 was used. Battery characteristics (discharge capacity, cycle characteristics) were obtained in the same manner as in Example 10. ). The results are shown in Table 2.
- Example 12 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that the positive electrode current collector of Example 4 was used. Battery characteristics (discharge capacity, cycle characteristics) were obtained in the same manner as in Example 10. ). The results are shown in Table 2.
- Example 13 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that the positive electrode current collector in Example 5 was used. Battery characteristics (discharge capacity, cycle characteristics) were obtained in the same manner as in Example 10. ). The results are shown in Table 2.
- Example 14 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that the positive electrode current collector in Example 6 was used. Battery characteristics (discharge capacity, cycle characteristics) were obtained in the same manner as in Example 10. ). The results are shown in Table 2.
- Example 15 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that the positive electrode current collector in Example 7 was used. Battery characteristics (discharge capacity, cycle characteristics) were obtained in the same manner as in Example 10. ). The results are shown in Table 2.
- Comparative Example 1 A positive electrode laminate and a coin-type lithium secondary battery were produced in the same manner as in Example 10 except that an aluminum foil without a conductive protective layer was used, and battery characteristics (discharge capacity, Cycle characteristics were investigated.
- Comparative Example 2 A solution was prepared by dissolving 0.03 mol ⁇ dm ⁇ 3 of 1,2,4-triazole in a mixed solvent of ethylene carbonate / dimethoxyethane (50/50% by volume). Next, after immersing the positive electrode laminate produced in Comparative Example 1 in the solution, it was taken out, and a coin-type lithium secondary battery was produced in the same manner as in Example 10 using the positive electrode laminate. The battery characteristics (discharge capacity, cycle characteristics) were examined in the same manner as in Example 10. The results are shown in Table 2.
- Comparative Example 3 A protective layer made of polyparaphenylene having a thickness of 10 ⁇ m was formed on both surfaces of the aluminum foil current collector by low-temperature firing.
- the positive electrode mixture slurry of Example 10 was applied on the aluminum foil current collector on which the protective layer was formed, and a coin-type lithium secondary battery was produced in the same manner as in Example 10.
- the battery characteristics (discharge capacity, cycle characteristics) were investigated. The results are shown in Table 2.
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Abstract
Description
変性PTFEは、他のモノマーに基づく重合単位が1モル%未満の重合体である。
本発明に用いる導電性フィラー(b)は、体積抵抗率が1×10-9~1Ω・cmのフィラーである。好ましい体積抵抗率は1×10-8~1×10-1Ω・cmである。
導電性カーボンフィラーと金属系フィラーとの組合せとしては、粒子状カーボンフィラーと粒子状及び/又は繊維状の金属系フィラーとの組み合わせ、繊維状カーボンフィラーと粒子状及び/又は繊維状の金属系フィラーとの組み合わせであり、要求性能に応じて適宜選択する。また、混合比も各フィラーの導電性の程度や重量、生成した導電層の弾性、柔軟性などを考慮して適宜選定すればよい。
乾燥工程の短縮、低温化の観点からは、溶剤は、水、又は、水と有機溶剤との混合溶剤が好ましく、水であることがより好ましい。
カーボンの分散性向上の観点からは、溶剤は、有機溶剤、又は、水と有機溶剤との混合溶剤が好ましく、有機溶剤であることがより好ましい。
溶剤の量は、塗装に適切な濃度となる量であればよい。
PTFE水性分散体(a)としては、乳化重合で得られたPTFE水性分散体(ディスパージョン)が好ましい。水性分散体中のPTFE粒子は一次粒子(平均粒径が0.1~0.5μm)として分散していることが好ましい。
また、PTFE水性分散体(a)を有機溶剤に転相してオルガノゾルとして、その後、導電性フィラー(b)を加えてもよい。この場合、溶剤は、有機溶剤、又は、水と有機溶剤との混合溶剤である。
本発明の導電性保護層形成用ペーストから形成される導電性保護層(A)は、集電体を保護するために設けられるものであり、集電体と電極合剤層(C)との間に設けられる層であることが好ましい。
(株)ミツトヨ製のクイックマクロMDQ-30Mを用いて測定する。
三菱化学アナリテック(株)製のLoresta-GPを使用し、4端子法で体積抵抗率を測定する。
集電積層体を0.5×0.7cmの大きさに切断し、ニッケル線を抵抗溶接で溶接してCV用の電極を作製する。また、測定用の電解液としては、エチレンカーボネート(EC)/メチルエチルカーボネート(MEC)(=30/70体積%)の電解質塩溶解用溶媒に電解質塩としてLiPF6を1.0モル/リットルの濃度となるように加えた電解液を使用する。
PTFE水性ディスパージョン(ダイキン工業(株)製D210C)(a)を固形分濃度20質量%に調整したPTFE水性分散体100gに、導電性フィラー(b)としてのアセチレンブラック(平均粒子径35nm)を50g、増粘剤としてアクリル系樹脂(A10H)を2g入れて導電性保護層形成用ペーストを調製した。ついで、このペーストを正極集電体(厚さ15μmのアルミニウム箔)上に均一に塗布し、片面に導電性含フッ素樹脂層(厚さ5μm)を形成し、熱風乾燥機で80℃にて10分間乾燥した。また、反対(裏)面にも同様にして調製したペーストを塗布して乾燥したのち、プレスを行い、両面に導電性含フッ素樹脂層(合計厚:10μm)を形成し、真空乾燥機で真空に引いたのち、120℃にて1時間乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
導電性保護層が形成されていないアルミニウム箔について、実施例1と同様に酸化電位を測定した。結果を図1に示す。
PTFE水性ディスパージョン(ダイキン工業(株)製D210C)(a)とFEP水性ディスパージョン(ダイキン工業(株)製ND110)を固形分比率(質量比)で6/4に混合し、ついで固形分濃度20質量%に調整した水性分散体100gを調製した。導電性フィラー(b)としてのアセチレンブラック(平均粒子径35nm)を50g、増粘剤としてカルボキシメチルセルロース(CMC)を1g入れて導電性保護層形成用ペーストを調製した。ついで、このペーストを正極集電体(厚さ15μmのアルミニウム箔)上に均一に塗布し、片面に導電性含フッ素樹脂層(厚さ5μm)を形成し、熱風乾燥機で80℃にて10分間乾燥した。また、反対(裏)面にも同様にして調製したペーストを塗布して乾燥したのち、プレスを行い、両面に導電性含フッ素樹脂層(合計厚:10μm)を形成し、真空乾燥機で真空に引いたのち、250℃にて10時間乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
PTFE水性ディスパージョン(ダイキン工業(株)製D210C)(a)とFEP水性ディスパージョン(ダイキン工業(株)製ND110)を固形分比率(質量比)で6/4に混合し、ついで、メチルイソブチルケトン(MIBK)に転相し、さらに固形分濃度20質量%に調整したオルガノゾルを100g調製した。これに導電性フィラー(b)としてのアセチレンブラック(平均粒子径35nm)を50g入れて導電性保護層形成用ペーストを調製した。ついで、このペーストを正極集電体(厚さ15μmのアルミニウム箔)上に均一に塗布し、片面に導電性含フッ素樹脂層(厚さ5μm)を形成し、熱風乾燥機で80℃にて10分間乾燥した。また、反対(裏)面にも同様にして調製したペーストを塗布して乾燥したのち、プレスを行い、両面に導電性含フッ素樹脂層(合計厚:10μm)を形成し、真空乾燥機で真空に引いたのち、250℃にて10時間乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
実施例2において、アセチレンブラックに代えてケッチェンブラックを用いたほかは同様の方法で導電性保護層形成用ペーストを調製し、実施例2と同様にして正極集電体(厚さ15μmのアルミニウム箔)に塗布し乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
実施例2において、アセチレンブラックに代えて気相法炭素繊維(平均繊維長:15μm、平均繊維径:150nm。昭和電工(株)製のVGCF(登録商標))を用いたほかは同様の方法で導電性保護層形成用ペーストを調製し、実施例2と同様にして正極集電体(厚さ15μmのアルミニウム箔)に塗布し乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
実施例2において、アセチレンブラックの配合量を150gに変更したほかは同様の方法で導電性保護層形成用ペーストを調製し、実施例2と同様にして正極集電体(厚さ15μmのアルミニウム箔)に塗布し乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
実施例2において、アセチレンブラックの配合量を2.5gに変更したほかは同様の方法で導電性保護層形成用ペーストを調製し、実施例2と同様にして正極集電体(厚さ15μmのアルミニウム箔)に塗布し乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
PTFE水性ディスパージョン(ダイキン工業(株)製D210C)(a)とP(TFE-VDF)〔TFE-VdF共重合体〕水性ディスパージョン(ダイキン工業(株)製VT470)を固形分比率(質量比)で6/4に混合し、ついで、メチルイソブチルケトン(MIBK)に転相し、さらに固形分濃度20質量%に調整したオルガノゾルを100g調製した。これに導電性フィラー(b)としてのアセチレンブラック(平均粒子径35nm)を50g入れて導電性保護層形成用ペーストを調製した。ついで、このペーストを正極集電体(厚さ15μmのアルミニウム箔)上に均一に塗布し、片面に導電性含フッ素樹脂層(厚さ5μm)を形成し、熱風乾燥機で80℃にて10分間乾燥した。また、反対(裏)面にも同様にして調製したペーストを塗布して乾燥したのち、プレスを行い、両面に導電性含フッ素樹脂層(合計厚:10μm)を形成し、真空乾燥機で真空に引いたのち、250℃にて10時間乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
PTFE水性ディスパージョン(ダイキン工業(株)製D210C)(a)とP(TFE-VDF)水性ディスパージョン(ダイキン工業(株)製VT470)を固形分比率(質量比)で8/2に混合し、ついで、N-メチルピロリドン(NMP)に転相し、さらに固形分濃度20質量%に調整したオルガノゾルを100g調製した。これに導電性フィラー(b)としてのアセチレンブラック(平均粒子径35nm)を50g入れて導電性保護層形成用ペーストを調製した。ついで、このペーストを正極集電体(厚さ15μmのアルミニウム箔)上に均一に塗布し、片面に導電性含フッ素樹脂層(厚さ5μm)を形成し、熱風乾燥機で80℃にて10分間乾燥した。また、反対(裏)面にも同様にして調製したペーストを塗布して乾燥したのち、プレスを行い、両面に導電性含フッ素樹脂層(合計厚:10μm)を形成し、真空乾燥機で真空に引いたのち、250℃にて10時間乾燥し、導電性保護層が両面に形成された正極集電積層体を作製した。得られた正極集電積層体について、体積抵抗率を測定した。結果を表1に示す。
実施例1で作製した本発明の正極集電積層体上にLiNi1/3Mn1/3Co1/3O2とカーボンブラックとポリフッ化ビニリデン(呉羽化学(株)製。商品名KF-1000)を90/3/7(質量%比)で混合した正極活物質をN-メチル-2-ピロリドンに分散してスラリー状とした正極合剤スラリーを均一に塗布し、乾燥して正極合剤層(厚さ50μm)を形成し、その後、ローラプレス機により圧縮成形して、正極積層体を製造した。
正極積層体を打ち抜き機で直径1.6mmの大きさに打ち抜き、円状の正極を作製する。
コイン型リチウム二次電池について、つぎの要領で放電容量とサイクル特性を調べた。
充放電電流をCで表示した場合、5mAを1Cとして以下の充放電測定条件で測定を行う。評価は、比較例1の放電容量の結果を100とした指数で行う。
充電:1.0C、4.7Vにて充電電流が1/10Cになるまでを保持(CC・CV充電)
放電:1C 3.0Vcut(CC放電)
サイクル特性については、上記の充放電条件(1.0Cで4.7Vにて充電電流が1/10Cになるまで充電し1C相当の電流で3.0Vまで放電する)で行う充放電サイクルを1サイクルとし、最初の5サイクル後の放電容量と100サイクル後の放電容量を測定する。サイクル特性は、つぎの計算式で求められた値をサイクル維持率の値とする。
サイクル維持率(%)=100サイクル放電容量(mAh)/5サイクル放電容量(mAh)×100
実施例2の正極集電体を用いたほかは実施例10と同様にして、正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
実施例4の正極集電体を用いたほかは実施例10と同様にして、正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
実施例5の正極集電体を用いたほかは実施例10と同様にして、正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
実施例6の正極集電体を用いたほかは実施例10と同様にして、正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
実施例7の正極集電体を用いたほかは実施例10と同様にして、正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
導電性保護層を形成していないアルミニウム箔を用いた以外は実施例10と同様にして正極積層体及びコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。
エチレンカーボネート/ジメトキシエタン(50/50体積%)の混合溶媒に、1,2,4-トリアゾールを0.03mol・dm-3を溶解した溶液を調製した。ついで、その溶液の中に比較例1で作製した正極積層体を浸漬させた後、取り出し、その正極積層体を使用して実施例10と同様にしてコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
アルミニウム箔集電体の両面に低温焼成により厚さが10μmのポリパラフェニレン製の保護層を形成した。その、保護層を形成させたアルミニウム箔集電体の上に実施例10の正極合剤スラリーを塗布し、実施例10と同様にしてコイン型リチウム二次電池を製造し、実施例10と同様にして電池特性(放電容量、サイクル特性)を調べた。結果を表2に示す。
Claims (16)
- ポリテトラフルオロエチレンと導電性フィラー(b)とを含む集電体保護用の導電性保護層形成用ペースト。
- 更に、溶剤を含む請求項1記載の集電体保護用の導電性保護層形成用ペースト。
- さらにテトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリアミドイミド、ポリイミド、ポリフッ化ビニリデン、及び、テトラフルオロエチレン-フッ化ビニリデン共重合体からなる群より選択される少なくとも1種の重合体を含む請求項2記載の導電性保護層形成用ペースト。
- 前記導電性フィラー(b)が、粒子状フィラー、繊維状フィラー、またはこれらの組合せである請求項2又は3記載の導電性保護層形成用ペースト。
- 前記導電性フィラー(b)が、導電性カーボンフィラーである請求項2~4のいずれかに記載の導電性保護層形成用ペースト。
- ポリテトラフルオロエチレン100質量部に対して導電性フィラー(b)が5~1000質量部含まれている請求項2~5のいずれかに記載の導電性保護層形成用ペースト。
- ポリテトラフルオロエチレン水性分散体(a)と導電性フィラー(b)を含む請求項1記載の集電体保護用の導電性保護層形成用ペースト。
- さらにテトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリアミドイミド、ポリイミド、ポリフッ化ビニリデン、及び、テトラフルオロエチレン-フッ化ビニリデン共重合体からなる群より選択される少なくとも1種の重合体を含む請求項7記載の導電性保護層形成用ペースト。
- 前記導電性フィラー(b)が、粒子状フィラー、繊維状フィラー、またはこれらの組合せである請求項7又は8記載の導電性保護層形成用ペースト。
- 前記導電性フィラー(b)が、導電性カーボンフィラーである請求項7~9のいずれかに記載の導電性保護層形成用ペースト。
- 前記ポリテトラフルオロエチレン分散体(a)中のポリテトラフルオロエチレン(固形分)100質量部に対して導電性フィラー(b)が5~1000質量部含まれている請求項7~10のいずれかに記載の導電性保護層形成用ペースト。
- 請求項1~11のいずれかに記載の導電性保護層形成用ペーストを塗布して得られる導電性保護層(A)が集電体(B)上に設けられてなる集電積層体。
- 前記導電性保護層(A)の体積抵抗率が0.001~50Ω・cmである請求項12記載の集電積層体。
- 請求項12または13記載の集電積層体の導電性保護層(A)上に、電極合剤層(C)が設けられてなる電極積層体。
- 正極、負極および非水電解液を備え、正極および負極の少なくとも一方が請求項14記載の電極積層体であるリチウム二次電池。
- 正極、負極および非水電解液を備え、正極および負極の少なくとも一方が請求項14記載の電極積層体である電気二重層キャパシタ。
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CN105074978A (zh) * | 2013-02-21 | 2015-11-18 | 东洋油墨Sc控股株式会社 | 导电性组合物、蓄电装置用带有基底层的集电体、蓄电装置用电极以及蓄电装置 |
WO2014167765A1 (ja) * | 2013-04-10 | 2014-10-16 | 株式会社豊田自動織機 | ポリテトラフルオロエチレン含有バインダー層を有する電極 |
JP2015038818A (ja) * | 2013-04-10 | 2015-02-26 | 株式会社豊田自動織機 | ポリテトラフルオロエチレン含有バインダー層を有する電極 |
WO2014171415A1 (ja) * | 2013-04-19 | 2014-10-23 | 東洋インキScホールディングス株式会社 | 導電性組成物、下地層形成用導電性組成物、蓄電デバイス用下地層付き集電体、蓄電デバイス用電極、および蓄電デバイス |
JP2015026595A (ja) * | 2013-04-19 | 2015-02-05 | 東洋インキScホールディングス株式会社 | 導電性組成物、蓄電デバイス用下地層付き集電体、蓄電デバイス用電極、及び蓄電デバイス |
CN105144435A (zh) * | 2013-04-19 | 2015-12-09 | 东洋油墨Sc控股株式会社 | 导电性组合物、基底层形成用导电性组合物、蓄电装置用带有基底层的集电体、蓄电装置用电极以及蓄电装置 |
KR20150144769A (ko) * | 2013-04-19 | 2015-12-28 | 토요잉크Sc홀딩스주식회사 | 도전성 조성물, 하지층 형성용 도전성 조성물, 축전 디바이스용 하지층 부착 집전체, 축전 디바이스용 전극 및 축전 디바이스 |
KR102151613B1 (ko) | 2013-04-19 | 2020-09-03 | 토요잉크Sc홀딩스주식회사 | 도전성 조성물, 하지층 형성용 도전성 조성물, 축전 디바이스용 하지층 부착 집전체, 축전 디바이스용 전극 및 축전 디바이스 |
JP2016134217A (ja) * | 2015-01-16 | 2016-07-25 | 東洋インキScホールディングス株式会社 | 導電性組成物、蓄電デバイス用下地層付き集電体、蓄電デバイス用電極、及び蓄電デバイス |
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KR20130056902A (ko) | 2013-05-30 |
US20130143117A1 (en) | 2013-06-06 |
JP2012084523A (ja) | 2012-04-26 |
KR101611677B1 (ko) | 2016-04-11 |
JP5168395B2 (ja) | 2013-03-21 |
US9373848B2 (en) | 2016-06-21 |
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