WO1996013873A1 - Cellule secondaire non aqueuse et son procede de fabrication - Google Patents
Cellule secondaire non aqueuse et son procede de fabrication Download PDFInfo
- Publication number
- WO1996013873A1 WO1996013873A1 PCT/JP1995/002205 JP9502205W WO9613873A1 WO 1996013873 A1 WO1996013873 A1 WO 1996013873A1 JP 9502205 W JP9502205 W JP 9502205W WO 9613873 A1 WO9613873 A1 WO 9613873A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- negative electrode
- mixture
- secondary battery
- positive electrode
- sheet
- Prior art date
Links
Classifications
-
- 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
- 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
- H01M4/621—Binders
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/49115—Electric battery cell making including coating or impregnating
Definitions
- Non-aqueous secondary battery and method of manufacturing the same are non-aqueous secondary battery and method of manufacturing the same
- the present invention relates to a non-aqueous secondary battery having improved charge / discharge characteristics such as discharge potential, discharge capacity and charge / discharge cycle life, and more particularly to a non-aqueous secondary battery having an electrode using a water-dispersible mixture paste.
- the present invention relates to a secondary battery and a manufacturing method thereof.
- the positive electrode active material or negative electrode material which is a compound capable of inserting and releasing lithium, is dispersed in a dispersion medium using a dispersing machine such as a homogenizer or a planetary mixer together with a conductive agent and a binder to form a dispersed paste.
- An electrode sheet is manufactured by applying the dispersion paste on a current collector and drying.
- a non-aqueous solvent is often selected as the dispersion medium, in order to avoid direct deterioration of the active material due to water and deterioration of battery performance due to residual moisture when the battery is assembled.
- an organic solvent there are problems such as working environment, environmental problems such as discharge, and difficulty in forming a uniform film.
- Positive and negative electrode materials especially negative electrode materials, which are compounds that can insert and release lithium, are not stable in water, and have a negative effect on the discharge capacity of non-aqueous secondary batteries and the charge / discharge cycleability.
- Japanese Unexamined Patent Publications Nos. 11-96567, 3-145,711, 3-64860 each disclose a method of pre-washing the active material with water. ing. However, these methods do not sufficiently improve the discharge characteristics. The reason why the charge / discharge cycle deteriorates when a water-dispersible mixture paste is used has not yet been clarified, but in addition to the reasons mentioned above, other factors that increase the internal resistance of the battery during cycling It is suggested that there is.
- a first object of the present invention is to provide a discharge potential, a discharge capacity, a charge / discharge cycle life, and the like.
- a second object of the present invention is to provide a non-aqueous secondary battery having improved charge / discharge characteristics and a method of manufacturing the same.
- a third object of the present invention is to provide a method for producing a water base of a mixture having improved dispersibility and a non-aqueous secondary battery using the same.
- a fourth object of the present invention is to provide a non-aqueous secondary battery having an optimum thickness using a mixture having improved dispersibility and a method for producing the same.
- An object of the present invention is to provide a non-aqueous secondary battery in which a non-aqueous electrolyte containing a positive electrode, a negative electrode, and a lithium salt capable of inserting and extracting lithium is accommodated in a battery container, and at least an active material capable of inserting and extracting lithium, and In the production of at least one of the electrodes obtained by applying and drying a water-dispersed mixture base containing at least one or more conductive agents made of a carbon compound on a current collector, at least one of the conductive agents
- the present invention has been achieved by a method for manufacturing a nonaqueous secondary battery, characterized by using an electrode prepared from the aqueous dispersion mixture paste using a dispersion liquid in which seeds are dispersed in water in advance together with a dispersing aid.
- a non-aqueous secondary battery comprising a positive electrode and a negative electrode capable of inserting and extracting lithium and a non-aqueous electrolyte containing a lithium salt in a battery container, comprising at least an active material capable of inserting and extracting lithium, and a carbon compound.
- At least one of the electrodes obtained by applying and drying an aqueous dispersion mixture paste containing at least one or more conductive agents on a current collector, at least one of the conductive agents together with a dispersing agent is used in advance.
- a method for producing a non-aqueous secondary battery comprising using an electrode prepared from the aqueous dispersion mixture base using a dispersion liquid dispersed in water.
- a method for producing a negative electrode comprising applying and drying an aqueous dispersion mixture paste containing at least an active material capable of inserting and extracting lithium onto a current collector, wherein the pH of the aqueous dispersion mixture paste is 5 or more. 10.
- a method for producing a negative electrode sheet for a non-aqueous secondary battery which is not more than 10.
- a water-dispersed mixture base containing at least one kind of conductive agent on a current collector and drying are housed in a battery container.
- at least one of the positive electrode sheet and the negative electrode sheet at least one of the conductive agent and the dispersing agent is dispersed in water in advance.
- a non-aqueous secondary battery comprising an electrode sheet prepared from a dispersed mixture paste.
- At least a positive electrode sheet and a negative electrode sheet obtained by applying a water-dispersed mixture paste containing at least an active material capable of inserting and extracting lithium and one or more conductive agents made of a carbon compound on a current collector, and drying. And a non-aqueous electrolyte containing a lithium salt and a non-aqueous electrolyte in a battery container, wherein the pH of the water-dispersing paste used for the negative electrode sheet is 5 or more and 10 or less. Water secondary battery.
- the thickness of the mixture on one side of the negative electrode during battery assembly Is 5 to 80 m, and the thickness of the mixture on one side of the positive electrode is 90 to 180 jtzm.
- the thickness of the mixture on one side of the negative electrode during battery assembly Is 5 to 80 m, and the thickness of the mixture on one side of the positive electrode is 90 to 180 // m, wherein the thickness of the mixture according to any one of the above (3) to (5) is Water secondary battery.
- the transition metal at least one is in the L i a MO b (wherein M of the positive electrode active material contained in the positive electrode mixture, containing at least one is C o, Mn, N i, V, and F e,
- M of the positive electrode active material contained in the positive electrode mixture containing at least one is C o, Mn, N i, V, and F e
- At least one kind of the negative electrode active material contained in the negative electrode mixture has a periodic rule.
- the above-mentioned (3) which is a compound selected from oxides and chalcogen compounds containing one or more elements selected from Tables IIIA, IVA and VA.
- the non-aqueous secondary battery according to any one of the items (1) to (6).
- the thickness of the mixture on one surface of the negative electrode is 10 to 80 // m
- the thickness of the mixture on one surface of the positive electrode is 100 to 170 // m.
- M 2 represents at least one selected from Ge, Pb, Bi, Sb, P, B, Al, and As, and 0, l ⁇ p + q ⁇ 4, 0.05.p ⁇ 2. , 1. 1 ⁇ r ⁇ 10 (18)
- FIG. 1 is a cross-sectional view of a cylindrical battery used in Examples.
- Insulation sealing body made of polypropylene
- Negative electrode can (battery can) doubles as negative electrode terminal
- the sheet-like positive and negative electrodes are prepared by dispersing a positive electrode mixture or a negative electrode mixture in water.
- the paste is made by coating the paste on a sheet-like current collector.
- the positive electrode active material or negative electrode material which is a compound capable of inserting and extracting lithium
- the positive electrode or negative electrode mixture also contains a conductive agent, a binder, a dispersing aid, a filler, and an ion conductive material, respectively. Agents, pressure boosters and various additives.
- Examples of the method of adjusting the water-dispersible mixture paste include a method in which these substances are added and dispersed in water at a time, a method in which a dispersing aid is dispersed in water in advance, and a conductive agent is added thereto and dispersed. Any of the following methods can be used: pre-mixing the dispersing agent or dispersing agent and then dispersing it in water.
- the conductive agent is mixed or kneaded with a liquid dispersing agent or a highly concentrated solution of the dispersing agent and then dispersed in water. The method is preferred.
- a mixing stirrer such as a kneader, a mixer, a homogenizer, a dissolver, a planetary mixer, a paint shaker, and a sand mill
- a mixing stirrer such as a kneader, a mixer, a homogenizer, a dissolver, a planetary mixer, a paint shaker, and a sand mill
- the conductive agent comprising a carbon compound that can be used in the present invention include natural graphite such as flaky graphite, flaky graphite and earthy graphite, graphites such as artificial graphite, channel black, furnace black, lamp black, and thermal black.
- carbon blacks such as acetylene black and Ketjen black, and carbon fibers. Of these, carbon black is more preferred, and acetylene black is particularly preferred.
- acetylene black is particularly excellent in conductivity and electrolyte permeability, and is a good conductive agent.However, on the other hand, acetylene black has poor wettability with water. It is difficult to disperse well in the mixture paste. Furnace black, graphite and the like are more excellent in dispersibility in an organic solvent, but have high cohesiveness in water and are not sufficiently dispersible.
- Japanese Patent Application Laid-Open No. 2-158055 discloses a method in which a manganese dioxide active material and a conductive agent of carbon powder are mixed in advance to form a mixed powder, and then a mixture paste for coating is prepared. ing. However, even with this method, the dispersibility of the conductive agent in water is remarkably inferior to that of the active material. The dispersion state of the conductive agent is still insufficient, and the conductive agent partially forms aggregates in the dispersed paste.
- a fatty acid having 6 to 22 carbon atoms (eg, caproic acid, caprylic acid, caproic acid, lauric acid, myristic acid, palmitic acid, stearic acid) Acid, behenic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearolic acid, etc.), the above fatty acids and alkali metals (Li, Na, K, etc.) or alkaline earth metals (Mg, Ca, Ba), metal couplings such as aliphatic amines, silane coupling agents, titanium coupling agents, higher alcohols, polyalkylene oxide phosphate esters, alkyl phosphate esters, alkyl borate esters, Compounds such as sarcosinates, polyalkylene oxide esters, lecithin, alkylenoxide, glyce Non
- Examples include water-soluble polymers such as polyvinyl alcohol or modified products thereof, polyacrylamide, polyhydroxy (meth) acrylate, and styrene-maleic acid copolymer.
- water-soluble polymers such as carboxymethylcellulose or less are preferable because the conductive agent composed of a carbon compound is dispersed particularly well, and carboxymethylcellulose, polyvinyl alcohol or a modified product thereof, and a styrene-maleic acid copolymer are particularly preferable.
- These dispersing aids can be used alone or in combination of two or more.
- a known dispersing machine and a known dispersing method such as a mixer and a homoplenderer can be used.
- These conductive agent dispersions can be used in the preparation of both positive and negative electrode sheets, but it is preferable to use them for both electrodes to form a battery.
- carbon compounds can be used alone or in combination of two or more.
- conductive fibers such as metal fibers, metal powders such as copper, nickel, aluminum and silver; conductive whiskers such as zinc oxide and potassium titanate; titanium oxide;
- An organic conductive material such as a conductive metal oxide or a polyphenylene derivative can be used alone or in combination as a mixture thereof.
- the amount of the conductive agent made of a carbon compound is not particularly limited, but is preferably 1 to 50% by weight, particularly preferably 2 to 30% by weight in the mixture of each electrode.
- the amount of the dispersing agent is not particularly limited, but is preferably 1 to 50% by weight, and more preferably 2 to 20% by weight, based on the amount of the conductive agent. If the amounts of these conductive agents and dispersion aids are too large, the electrode volume will increase and the capacity per unit volume or unit weight of the electrode will decrease, and if too small, the conductivity or dispersibility of the conductive agent will decrease, The capacity decreases.
- the total amount is preferably within this range.
- a non-aqueous secondary battery with excellent charge / discharge characteristics such as discharge capacity and cycle life can be obtained by adjusting the pH of the water-dispersed mixture paste adjusted when manufacturing the negative electrode to an appropriate range.
- the pH of the water-dispersed mixture paste is included in the negative electrode material, conductive agent, binder, dispersant, filler, ionic conductive agent, and pressure increase It depends on the type and amount of the agent and various additives. By appropriately selecting and adjusting these, a water-dispersed mixture paste having a preferable pH can be obtained, and the nonaqueous secondary battery can have excellent charge / discharge characteristics.
- the preferable range of pH is 5 or more and 10 or less, more preferably 5.5 or more and 9.5 or less, and further preferably 6 or more and 9 or less.
- the pH of the aqueous dispersion mixture paste may be adjusted by adding a pH regulator.
- the pH adjuster may be added simultaneously with the mixture component, or may be added later to the completed water-dispersed mixture paste.
- Acids include sulfuric acid, hydrochloric acid, nitric acid, nitric acid, oxalic acid, moth acid, etc.
- alkalis include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, sodium hydrogen carbonate, ammonia, etc. Can be used.
- a preferred temperature range is 5 ° C or more and 80 ° C or less, more preferably 5 ° C or more and 50 ° C or less.
- a preferred time range is within 7 days, more preferably within 4 days.
- the preferable thickness of the mixture of the positive and negative electrodes which does not impose a burden on any one of the positive and negative electrodes and shortens the charge / discharge cycle life, is 5 to 5 when the battery is assembled. 80 i / m, and the thickness of the mixture on one surface of the positive electrode is 90 to 180 m. More preferably, the thickness of the mixture on one side of the negative electrode is 10 to 80 m, and the thickness of the mixture on one side of the positive electrode is 100 to 180 m.
- a negative electrode material As the compound capable of inserting and releasing lithium (hereinafter, referred to as a negative electrode material) used in the negative electrode sheet of the present invention, a carbonaceous compound, an inorganic oxide, an inorganic chalcogenide, and an organic polymer compound are preferable. These may be used alone or in combination. For example, a combination of a carbonaceous compound and an inorganic oxide is exemplified. These negative electrode materials are preferable because they provide high capacity, high discharge potential, high safety, and high cycle effects.
- the carbonaceous compound is selected from natural graphite, artificial graphite, vapor-grown carbon, organically calcined carbon, and the like, and preferably contains a graphite structure. Further, the carbonaceous compound may contain 0 to 10% by weight of a heterogeneous compound, for example, B, P, N, S, SiC, B4C, in addition to carbon.
- a heterogeneous compound for example, B, P, N, S, SiC, B4C
- Examples of the element forming the inorganic oxide or the inorganic chalcogenide include a transition metal, a metal belonging to Groups 13 to 15 of the periodic table, and a metalloid element.
- transition metal compound a single or composite oxide of V, Ti, Fe, Mn, Co, Ni, Zn, W and Mo, or chalcogenide is particularly preferable.
- organic polymer compound polyacene, polyacetylene, polypyrrole, and derivatives thereof which can be doped with lithium ions can be used.
- the negative electrode material preferably used in the present invention is an inorganic oxide or an inorganic chalcogenide containing a Group 13 to Group 15 element of the Periodic Table, and the Group 13 to Group 15 element of the Periodic Table is B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, As, Sb, Bi.
- These compounds include G e O, G eO 2 , S nO, S n S, S nO 2 ,
- the above-mentioned composite chalcogen compound and composite oxide are mainly amorphous when incorporated into a battery.
- amorphous as used herein means an X-ray diffraction method using CuK rays at a value of 20 to 40 from 20 °. It is a substance having a broad scattering band having a peak at the top, and may have a crystal diffraction line.
- the strongest intensity of the crystalline diffraction line observed at a value of 20 to 40 ° or more and 70 ° or less is the peak of a broad scattering band observed at a ⁇ ⁇ value of 20 ° or more and 40 ° or less.
- Diffraction line intensity It is preferably not more than 500 times, more preferably not more than 100 times, particularly preferably not more than 5 times, and most preferably not having a crystalline diffraction line.
- the compounds of the general formula (3) are more preferred.
- M 2 is the same as M 2 in general formula (2).
- p and Q represent 0.1 l ⁇ p + q ⁇ 4 and 0.05 ⁇ p ⁇ 21.1 r10.
- Examples of the complex oxides of the general formulas (1) to (3) include, but are not limited to, the following.
- a charge / discharge cycle characteristic is improved, a high discharge voltage and a high capacity are obtained.
- a non-aqueous secondary battery with high safety and excellent rapid charging characteristics can be obtained.
- a particularly excellent effect can be obtained when a compound containing Sn and having two valences of Sn is used as the negative electrode material.
- the valence of Sn can be determined by a chemical titration operation. For example, Physics and Chemistry of Glasses Vol.8 No.
- the metal Sn zero-valent Sn
- the metal Sn has a peak at an extremely low magnetic field around 7000 ppm with respect to Sn (CH 3 ) 4 ,
- group 1 elements (1 ⁇ 3,, 111), ji3), group 2 elements (Be, Mg, Ca, Sr, Ba), transition metals (Sc, Ti, V, C r, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanide metals, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg) and Group 17 elements of the periodic table (F, C1, Br, I) can be included. Further, it may contain a dopant of various compounds that increase electron conductivity (for example, compounds of Sb, In, and Nb).
- group 2 elements Be, Mg, Ca, Sr, Ba
- transition metals Sc, Ti, V, C r, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, lanthanide metals, Hf, Ta
- the amount of the compound to be added is preferably 0 to 20 mol%.
- a method for synthesizing the complex chalcogen compounds and complex oxides represented by the general formulas (1) to (3) in the present invention there are a firing method and a solution method, but the firing method is preferable. The firing method will be described below.
- the firing conditions are preferably a heating rate of not less than 4 ° C. per minute and not more than 2000 ° C., more preferably not less than 6 and not more than 2000. It is particularly preferably at least 10 ° C. and at most 200, and the firing temperature is preferably at least 250 and at most 150, more preferably at most 350.
- 0 ° C. or more and 150 ° C. or less particularly preferably 500 ° C. or more and 150 ° C. or less
- the firing time is 0.01 hour or more and 100 hours or less. It is preferred, more preferably not more than 5 hours or 7 0 h 0., a country preferably not more than 2 0 hours 1 hour or more, and as the cooling rate below per minute 2 ° C or more 1 0 7
- the heating rate in the present invention is the average rate of temperature rise from “50% of the firing temperature (in ° C)” to “80% of the firing temperature (in ° C)”. Is the average rate of temperature drop from "80% of firing temperature (indicated by ° C)" to "50% of firing temperature (indicated by)”.
- the temperature may be cooled in a baking furnace, or may be taken out of the baking furnace and put into, for example, water for cooling. Also ceramic processing (Gihodo Publishing)
- the firing gas atmosphere is preferably an atmosphere having an oxygen content of 5% by volume or less, and more preferably an inert gas atmosphere.
- the inert gas include nitrogen, argon, helium, krypton, and xenon.
- the average particle diameter (D) of the negative electrode active material of the present invention is 0.7 to 25 // m, Preferably, 60% or more of the total volume is 0.5 to 30 m. More preferably, the average particle size (D) is 0.8 to 20 m, and 75% or more of the total volume is 0.5 to 30 / m. Particularly preferably, the average particle size (D) is 1.0 to 16 / im, and 90% or more of the total volume is 0.5 to 30 zm. However, it goes without saying that the particle size of the negative electrode active material used does not exceed the thickness of the mixture on one side of the negative electrode.
- the average particle size as referred to herein is the median size of the primary particles, and is measured by a laser diffraction type particle size distribution measuring device.
- the volume occupied by the particle group having a particle size of 1 / m or less of the negative electrode active material of the present invention is 30% or less of the total volume
- the volume occupied by the particle group having a particle size of 20 / zm or more is the total volume. It is preferably at most 25%. More preferably, the volume occupied by the particle group having a particle size of 1 // m or less is 20% or less of the total volume, and the volume occupied by the particle group having a particle size of 20 m or more is 14% or less of the total volume. is there.
- the volume occupied by the particle group having a particle size of 1 or less is 10% or less of the total volume
- the volume occupied by the particle group having a particle size of 20 m or more is 10% or less of the total volume.
- the specific surface area of the negative electrode active material of the present invention is 0. 1 ⁇ 1 0 m 2 Zg, even more preferably from 0.1 to 81 ⁇ 2 8, particularly preferably 0. ZT rr ⁇ Zg is there.
- the measurement can be performed by the usual BET method.
- a method in which the calcined material or the coarsely pulverized material is pulverized and Z or classified.
- a grinding method a dry grinding method and a wet grinding method using a solvent as a medium are used.
- Solvents used in the wet pulverization method include, for example, water, toluene, xylene, methanol, ethanol, n-propanol, isopropyl alcohol, isobutyl alcohol, acetone, methyl ethyl ketone, Butyl acetate, N, N
- the amount of the solvent used is preferably 1/10 to 20 times, more preferably 1 to 5 to 10 times the powder material.
- the pulverization method is preferably a dry pulverization method or a wet pulverization method using Z or water as a medium.
- crushers include mortars, ball mills, circular vibrating ball mills, Vibration mill, surgical ball mill, planetary ball mill, swirling air jet mill, pot mill, centrifugal mill, tower mill, sand mill, attritor, centrimill, dyno mill, roller mill, pin mill, tube mill, rod mill, joyo
- a pulverization method using a swirling airflow type jet miner, a ball mill, or a vibrating ball mill is preferable.
- it is preferable to classify the particles to a predetermined particle size and an air classifier (for example, a cyclone) or a sieve is preferably used.
- the temperature for pulverization or classification is preferably 5 to 150 ° C, more preferably 10 to 90 ° C, depending on the material used and the type of solvent.
- the heat treatment atmosphere may be air, an inert gas atmosphere (eg, argon gas, nitrogen gas, helium gas, etc.), an active gas atmosphere such as an oxygen gas or a hydrogen gas, or a pressurized or reduced pressure atmosphere. Is in air, in an inert gas atmosphere, or in a reduced pressure atmosphere.
- the term “before forming the electrode mixture” as used herein means, for example, before mixing with a binder, a conductive agent, or the like, and indicates that heat treatment is performed only with the negative electrode active material.
- the time of the heat treatment is preferably from 90 to immediately before, and more preferably 30 to immediately before, which constitutes the electrode mixture.
- the heat treatment temperature is more preferably from 120 to 350 ° C, and particularly preferably from 150 to 300 ° C.
- the heat treatment time is preferably 0.5 to 120 hours, more preferably 1 to 80 hours, and particularly preferably 1 to 48 hours.
- the positive electrode active material used in the positive electrode sheet of the present invention may be any compound capable of inserting and extracting lithium ions, and is particularly selected from transition metal oxides and transition metal chalcogenides.
- transition metal oxides are preferable, and transition metal oxides containing lithium are particularly preferable.
- Preferred transition metals used in the present invention include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, and W.
- manganese dioxide, vanadium pentoxide, iron oxide, and monoxide Preference is given to molybdenum, molybdenum sulfide, cobalt oxide, iron sulfide and titanium sulfide. These compounds can be used alone or in combination of two or more. Further, it can be used as a transition metal oxide containing lithium.
- compounds that enhance ionic conductivity such as Ca 2+ , or amorphous network formers containing P, B, and Si (for example, P 20 5, L i P0 4, H 3 B0 3, B 2 0 3, S i 0 2 , etc.) and may be fired by mixing. Further, it may be mixed with an alkali metal ion such as Na, K, Mg or the like and / or a compound containing Si, Sn, A, Ga, Ge, Ce, In, Bi or the like, followed by firing.
- the transition metal oxide containing lithium can be synthesized, for example, by firing a mixture of a lithium compound and a transition metal compound.
- the positive electrode active material used in the present invention can be synthesized by a method in which a lithium compound and a transition metal compound are mixed and fired, or a solution reaction, but a firing
- the positive electrode active material obtained by firing is water, acidic aqueous solution, alkaline aqueous solution, It may be used after washing with a solvent.
- a method of chemically introducing lithium ions into the transition metal oxide a method of synthesizing lithium metal, a lithium alloy or butyllithium by reacting with the transition metal oxide may be used.
- the average particle size of the positive electrode active material used in the present invention is not particularly limited.
- the volume of 0.5 to 30 ⁇ m particles is 95% or more. More specifically, the volume occupied by the particle group having a particle size of 3 or less is 18% or less of the total volume, and the volume occupied by the particle group of 15 to 25 m is 18% or less of the total volume. More preferably, the volume occupied by the particle group having a particle size of 3 m or less is 17% or less of the total volume, and the volume occupied by the particle group having a size of 15 m or more and 25 m or less is the total volume.
- the volume occupied by the particle group having a particle size of 3 or less is 16% or less of the total volume and the volume occupied by the particle group having a particle size of 15 ⁇ m or more and 25 or less is more preferable. However, it must be less than 2% of the total volume.
- D (25%) 3 to 7 m
- D (50%) 3 to 7 m
- the positive electrode active material of the present invention does not substantially have a particle size distribution of 1 xm or less or 25 m or more.
- having substantially no particle size distribution means that the volume fraction of particles of 1 m or less or 25 m or more is 3% or less. More preferably, the volume fraction of particles of 25 m or more is 2% or less, and particularly preferably, the volume fraction of particles of 1 m or less or 25 m or more is 0%.
- the specific surface area is not particularly limited, it is preferably 0 8 ⁇ ⁇ ⁇ ⁇ 2 // g by the 8-patch method. 0. lm more preferably 2 // g to 2 0 m 2 Zg, further preferred properly is 0.1111 2 Bruno ⁇ 5111 2 Bruno g, particularly preferably 0. 2 m 2 / g ⁇ 1 n ⁇ Z g.
- the pH of the supernatant is preferably 7 or more and 12 or less.
- the calcination temperature is preferably 500 to 150, more preferably 700 to 120 ° C, and particularly preferably. It is 750 to 100 ° C.
- the firing time is preferably 4 to 30 hours, more preferably 6 to 20 hours, and particularly preferably 6 to 15 hours.
- the surface of the positive electrode active material or the negative electrode material of the oxide used in the present invention can be coated with an oxide having a chemical formula different from that of the positive electrode active material or the negative electrode material used.
- the surface oxide is preferably an oxide containing a compound that dissolves in both acidity and alkalinity.
- a metal oxide having high electron conductivity is preferable.
- dopant in P b 0 2, F e 2 0 3, S n 0 2, I n 2 0 3, etc. Z n 0 or child these oxides Bok e.g., different valency oxide Metal, a halogen element, etc.
- Particularly preferred are S i 0 2, S n 0 2, F e 2 0 3, Z n O, P b 0 2.
- the amount of the surface-treated metal oxide is preferably 0.1 to 10% by weight based on the positive electrode active material or the negative electrode material. Further, 0.2 to 5% by weight is particularly preferable, and 0.3 to 3% by weight is most preferable.
- the surface of the positive electrode active material or the negative electrode material can be modified.
- the surface of a metal oxide may be treated with an esterifying agent, treated with a chelating agent, or treated with a conductive polymer, polyethylene oxide, or the like.
- the surface of the negative electrode material can be modified.
- treatment may be performed by providing an ion-conductive polymer-polyacetylene layer.
- the positive electrode active material and the negative electrode material may be subjected to a purification step such as washing with water.
- a polysaccharide As the binder used in the water-dispersible paste of the present invention, a polysaccharide, a thermoplastic resin, a rubbery elastic polymer, or a mixture thereof can be used.
- Preferred examples are starch, polyvinyl alcohol, strength Ruboxyl cellulose, hydroxypropyl cellulose, regenerated cellulose, diacetyl cellulose, polyvinyl chloride, polyvinylpyrrolidone, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-dieneter
- examples include polymers (EPDM), sulfonated EPDM, styrene butadiene rubber, polybutadiene, fluororubber and polyethylene oxide.
- the amount of the binder added is not particularly limited, but is preferably 1 to 50% by weight, and particularly preferably 2 to 30% by weight.
- the distribution of the binder in the mixture may be uniform or non-uniform.
- the binder agent preferably used in the present invention is a polymer having a decomposition temperature of 30 (TC or more.
- the decomposition temperature is a temperature at which the weight of the polymer decreases when heated in vacuum.
- the decomposition temperature of polyethylene is 335 to 450.
- SL Madorsky et al. Used a thermobalance to accurately compare the thermal stability of polymers. Isothermal pyrolysis of the polymer in a vacuum to determine the relationship between the weight loss rate after 30 minutes and the temperature, and determine the half-life temperature (Th) at which the weight loss rate reaches 50% (for example, SPEJ, 17 windings) According to this, the polyethylene has a Th of 406 ° C.
- the decomposition temperature defined in the present invention corresponds to T. ⁇ Polymers having a decomposition temperature (Th) of at least 300 ° C. are preferred as the binder of the present invention.
- the resin include polyethylene, polypropylene, epoxy resin, polyester, fluorine resin, etc., and fluorine resin is particularly preferable.
- the fluorine resin is described in JIS690 “Plastic terms”. As described above, this is a general term for resins having a carbon-fluorine bond in the molecule of the polymer.
- PVDF Polyvinylidene fluoride
- FEP Tetrafluoroethylene-hexafluoropropylene copolymer
- the above polymer may be further copolymerized with another ethylenically unsaturated monomer.
- the copolymerizable ethylenically unsaturated monomers include, for example, acrylate, methacrylate, vinyl acetate, acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, butadiene, styrene, N-vinylpyrrolidone, N-
- the present invention is not limited to these, including vinyl pyridine, glycidyl methacrylate, hydroxymethyl methacrylate, and methyl vinyl ether.
- the filter can use any fibrous material that does not cause a chemical change in the constructed battery.
- polypropylene polymers, polyethylene-based polymers such as polyethylene, and fibers such as glass and carbon are used.
- the amount of the filler is not particularly limited, but is preferably 0 to 30% by weight.
- the ionic conductive agent those known as inorganic and organic solid electrolytes can be used, and the details are described in the section of the electrolytic solution.
- the pressure booster is a compound for increasing the internal pressure as described later, and carbonate is a typical example.
- the electrolyte is generally composed of a solvent and a lithium salt (anion and lithium cation) dissolved in the solvent. Solvents include propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, getyl carbonate, methylethyl carbonate, arbutyrolactone, methyl formate, methyl acetate, 1,2-dimethoxetane, and tetrahydrofuran.
- 2-methyltetrahydrofuran dimethylsulfoxide, 1,3 dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, ethyl monoglyme, phosphate triester, trimethoxymethane, dioxolane derivative, sulfolane, 3-methyl- Aprotic organic solvents such as 2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ethyl ether, and 1,3-propane sultone; One or a combination of two or more of these can be used.
- Lithium salt cations dissolved in these solvents include, for example, C 10 ⁇ , BF, PF 6 ⁇ , CF 3 SO, CF 3 C0 2- , As F 6- , SbF 6- , (CF 3 S0 2 ) 2 N ⁇ , B.o C 1-, (1,2-dimethoxetane) 2 CI O.-, Lower aliphatic carboxyl Acid ion, A 1 C 14 —, C 1-, Br—, I—, anion of a borane compound, and tetraphenyl borate ion; one or more of these may be used. it can. Especially, it is preferable to include a cyclic carbonate and a non-cyclic carbonate.
- getyl carbonate dimethyl carbonate, and methylethyl carbonate.
- ethylene carbonate and propylene carbonate are preferable to include getyl carbonate, dimethyl carbonate, and methylethyl carbonate.
- propylene carbonate Natick DOO, 1, 2-dimethyl Tokishe Tan, L i CF 3 S0 3 dimethyl carbonate or GETS chill carbonate appropriately mixed electrolyte, L i C 10 4, L i BF Electrolytes containing 4 and or L i PF 6 are preferred. In those supporting salt, it is particularly preferred to include L i PF 6.
- the amount of these electrolytes to be added to the battery is not particularly limited, but the required amount can be used depending on the amounts of the positive electrode active material and the negative electrode material and the size of the battery.
- the concentration of the supporting electrolyte is not particularly limited, but is preferably 0.2 to 3 mol per liter of the electrolytic solution.
- the following solid electrolyte can be used in combination.
- Solid electrolytes are classified into inorganic solid electrolytes and organic solid electrolytes.
- Well known inorganic solid electrolytes include Li nitrides, halides, and oxyacid salts. Among them, L i 3 N, L i I, L i 5 NI 2 , L i 3 N_L il-L i OH, L and S i 0 4 , L i 4 S i O ⁇ -L i o L i OH, x L i 3 PO *-(1-x) L i S 0, L i 2 S i S 3 , phosphorus sulfide compounds, etc. are effective.
- the organic solid electrolyte includes a polyethylene oxide derivative or a polymer containing the derivative, a polypropylene oxide derivative or a polymer containing the derivative, a polymer containing an ion dissociating group, a polymer containing an ion dissociating group, and A polymer matrix material containing a mixture of electrolytes, a phosphate ester polymer, and an aprotic polar solvent is effective. Furthermore, there is a method of adding polyacrylonitrile to the electrolyte. A method using both an inorganic and an organic solid electrolyte is also known.
- another compound may be added to the electrolyte for the purpose of improving the discharge / charge / discharge characteristics.
- pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, hexanoic acid triamide, ditrobenzene derivative, sulfur, quinonimine dye, N-substituted oxazolidinone and N, N '- substituted Lee Midarijinon, ethylene glycol di al kill ether, quaternary Anmoniumu salts, polyethylene glycol, pyrrole, 2-main butoxy ethanol, a 1 C 1 3, conductive polymer electrode active monomer material one, triethylene phosphoramide Amides, trialkylphosphines, morpholines, aryl compounds with carbonyl groups, crown ethers such as 12-crown-14, hexamethylphosphoric triamide and 4-alkylmorpholines, bicyclic Tertiary amine,
- a halogen-containing solvent such as carbon tetrachloride, Ethylene trifluoride chloride can be included in the electrolyte.
- carbon dioxide gas can be included in the electrolytic solution to make it suitable for high-temperature storage.
- the mixture of the positive electrode and the negative electrode can contain a lysate or an electrolyte.
- a method is known in which the ion-conductive polymer, nitromethane, and an electrolytic solution are included.
- an insulating microporous thin film having a high ion permeability, a predetermined mechanical strength, and an insulating property is used. Further, it is preferable to have a function of closing the holes at 80 ° C. or higher and increasing the resistance. Sheets and non-woven fabrics made of polyolefins such as polybrylene and Z or polyethylene or glass fibers due to their hydrophobicity and organic solvent resistance are used.
- a range generally used as a battery separator is used. For example, 0.01 to 1 O jwm is used.
- the thickness of the separator is generally used in the range of the battery separator. For example, 5 to 300 ⁇ m is used.
- the method of forming the pores may be a dry method, a drawing method, a solution, a solvent removing method, or a combination thereof.
- the current collector of the electrode active material any electronic conductor that does not cause a chemical change in the configured battery may be used.
- the positive electrode in addition to materials such as stainless steel, nickel, aluminum, titanium, and carbon, those obtained by treating the surface of aluminum or stainless steel with carbon, nickel, titanium, or silver are used. Particularly, aluminum or aluminum alloy is preferable.
- the anode is made of stainless steel, nickel, copper, titanium, aluminum, carbon, etc., as well as copper, stainless steel with carbon, nickel, titanium or silver treated on the surface, A 1 — C d alloy or the like is used. Particularly, copper or copper alloy is preferable. Oxidation of the surface of these materials is also used. In addition, it is desirable to make the current collector surface uneven by surface treatment.
- As the shape in addition to oil, a film, a sheet, a net, a punched thing, a glass body, a porous body, a foamed body, a molded body of a fiber group, and the like are used.
- the thickness is not particularly limited, but a thickness of 1 to 500 // m is used.
- Battery shape is coin, button, seat, cylinder, flat, corner Also applicable to
- a method for drying or dewatering pellet pellets generally employed methods can be used.
- hot air, vacuum, infrared rays, far infrared rays, electron beams and low-humidity air alone or in combination The temperature is preferably in the range of 80 to 350 ° C, particularly preferably in the range of 100 to 250 ° C.
- the water content of the whole battery is preferably 200 ppm or less, and the positive electrode mixture, the negative electrode mixture and the electrolyte are each preferably 500 ppm or less from the viewpoint of cycleability.
- a method for pressing pellets and sheets As a method for pressing pellets and sheets, a method generally used can be used, and a die press method and a calendar press method are particularly preferable.
- the pressing pressure is not particularly limited, but is preferably 0.2 to 3 tZcm 2 .
- the breathing speed in the calendar press method is preferably from 0.1 to 50 mZ.
- the pressing temperature is preferably room temperature to 200 ° C.
- the ratio of the width of the negative electrode sheet to the width of the positive electrode sheet is preferably 0.9 to 1.1. In particular, 0.95 to 0 is preferable.
- the content ratio between the positive electrode active material and the negative electrode material varies depending on the compound type and the mixture formulation, and thus cannot be limited. However, it can be set to an optimal value from the viewpoint of capacity, cycleability, and safety.
- a safety valve can be used as a sealing plate.
- various conventionally known safety elements may be provided. For example, fuses, bimetals, PTC elements, and the like are used as overcurrent prevention elements.
- a method of cutting the battery can a method of cracking a gasket, a method of cracking a sealing plate, or a method of cutting with a lead plate can be used.
- the charger may be provided with a protection circuit incorporating measures for overcharging or overdischarging, or may be connected independently.
- a method of interrupting the current by increasing the internal pressure of the battery can be provided.
- a compound capable of increasing the internal pressure can be contained in the mixture or the electrolyte. Examples of the compound raising the internal pressure, L i 2 C0 3, L i HC0 3, N a 2 C0 3, N a HC0 3, and carbonates, such as C a COa, MgC0 3 and the like.
- a metal or alloy having electrical conductivity can be used for the can or the lead plate.
- metals such as iron, nickel, titanium, chromium, molybdenum, copper, and aluminum or alloys thereof are used.
- Known methods eg, DC or AC electric welding, laser welding, ultrasonic welding
- Conventionally known compounds and mixtures such as asphalt can be used as the sealing agent for sealing.
- non-aqueous secondary battery of the present invention is not particularly limited.
- a color notebook computer a black-and-white notebook computer, a sub-note computer, a pen-input computer, a pocket (palm-top) computer
- Note-type word processor pocket word processor, e-book breaker, mobile phone, cordless phone handset, pager, handy terminal, mobile fax, mobile phone copy, mobile printer, headphone stereo, video movie, LCD TV, handy cleaner, portable CDs, minidiscs, electric shavers, electronic translators, car phones, transceivers, power tools, electronic organizers, calculators, memory cards, tape recorders, radios, backup power supplies, memory cards, etc. That.
- Other consumer products include automobiles, electric vehicles, motors, lighting equipment, toys, game machines, road conditioners, eyeglasses, watches, strobes, cameras, and medical equipment (pacemakers, captive devices, shoulder massagers, etc.) Is mentioned. Furthermore, it can be used for various types of munitions and space. It can also be combined with other secondary batteries, solar cells or primary cells.
- the preferred combination of the present invention is preferably a combination of the above-mentioned chemical materials and preferred components of battery components.
- the positive electrode current collector is made of stainless steel or aluminum, and has a net, sheet, foil, or lath shape.
- Anode materials include lithium metal, lithium alloy (Li-A1), carbonaceous compounds, and oxidized Things (L i CoV0 4, Sn0 2 , SnO, S i O, Ge0 2, GeO, S n S i 0 3, S n S i o. 3 A 1 0 ⁇ , B o 2 P o. 3 0 3. 2), sulfides (T i S 2, SnS 2 , SnS, Ge S 2, Ge S) it is preferred to use at least one compound, and the like.
- the negative electrode current collector is made of stainless steel or copper, and has a net, sheet, foil, lath, and other shapes.
- a carbon material such as acetylene black or graphite may be mixed as an electron conductive agent.
- a carbon material such as acetylene black or graphite may be mixed as an electron conductive agent.
- a carbon material such as acetylene black or graphite
- the binder fluorinated thermoplastic compounds such as polyvinylidene fluoride and polyfluoroethylene, polymers containing acrylic acid, styrene butadiene rubber, and elastomers such as ethylene propylene terpolymer can be used alone or in combination.
- ethylene carbonate as an electrolytic solution
- a combination of cyclic and non-cyclic carbonates such as getyl carbonate and dimethyl carbonate, or an ester compound such as ethyl diethyl carbonate, and Li PF 6 as a supporting electrolyte
- the separator polypropylene or polyethylene alone or a combination thereof is preferable.
- the battery can be in the form of coin, button, cylinder, flat or square. It is preferable that the battery is provided with a means (eg, an internal pressure release type safety valve, a current cutoff type safety valve, and a separator that increases resistance at high temperatures) to ensure safety against malfunction.
- the following compounds were used as active materials for the positive and negative electrodes, respectively. In each case, particles having a diameter exceeding 10 / im were removed by sieving.
- Acetylene black (Denka Black manufactured by Denki Kagaku Co., Ltd.) 10 parts by weight, 60 parts by weight of a 2% by weight aqueous solution of carboxymethylcellulose are premixed in a planetary mixer for 5 minutes, and 30 parts by weight of water are added.
- the conductive agent dispersion was prepared by further stirring and mixing for 20 minutes.
- This mixture paste is referred to as “positive electrode paste 1”.
- the mixture-dispersed pastes prepared using the positive electrode active materials (2) and (3) are referred to as a positive electrode paste 2 and a positive electrode paste 3, respectively.
- the mixture dispersion paste prepared in the same manner as the positive electrode paste 1 using the positive electrode active material (1) and sodium oleate as a dispersing agent is used as the positive electrode paste 4.
- a cathode paste 5 using polyacrylic acid as a dispersing aid is used.
- a mixture dispersion paste prepared in the same manner as the positive electrode paste 1 using graphite (Lonza Graphite KS-6) as a conductive agent is used as the positive electrode paste 6.
- This conductive agent dispersion 1 0 0 part by weight, the negative electrode active material (1); S i S n0 3 ( a mixture of S i 0 2 and S nO, calcined for 2 hours at 1 0 0 0 ° C in an argon atmosphere Synthesized, pulverized, with a center particle size of 2 m) in an amount of 200 parts by weight, 10 parts by weight of polyvinylidene fluoride as a binder, and 10 parts by weight of water, and stirred in a planetary mixer for 20 minutes. The mixture was stirred and mixed to obtain a negative electrode mixture paste. This mixture-dispersed paste is referred to as negative electrode paste 1.
- pastes prepared using the negative electrode active materials (2) to (17) are used as negative electrode pastes 2 to 17, respectively.
- a negative electrode paste 51 was prepared using the negative electrode active material (1) and a styrene-maleic acid copolymer as a dispersing aid, and prepared in the same manner as the negative electrode paste 1.
- a negative electrode paste 52 was prepared by using a modified polyvinyl alcohol (Kuraray Povar MP-103) as a dispersing aid.
- the preparation of the mixture having the same composition as the positive electrode mixture dispersion paste 1 of the present invention was carried out by a single stirring and mixing without preparing the dispersion of the conductive agent in advance. That is, acetylene 100 parts by weight of a rack, 60 parts by weight of a 2% by weight aqueous solution of carboxymethylcellulose, 200 parts by weight of a positive electrode active material; 200 parts by weight of LiCo02 (center particle size: 5 m), an aqueous dispersion of a binder ( (Solid content: 50% by weight) and 50 parts by weight of water were added thereto, followed by stirring and mixing for 60 minutes or 180 minutes in a planetary mixer to obtain a positive electrode mixture-dispersed paste. These are referred to as positive electrode pastes 101 and 102, respectively.
- the preparation of the mixture having the same composition as that of the negative electrode mixture dispersion paste 1 of the present invention was carried out by one stirring and mixing using the same mixer and without previously preparing the dispersion of the conductive agent. That acetylene black 1 0 part by weight, graphite (KS- 6) 2 0 parts by weight, concentration of 2 wt% carboxymethyl cellulose solution 5 0 parts by weight, an anode active material; the S i S n 0 3 2 0 0 parts by weight, 10 parts by weight of polyvinylidene fluoride and 30 parts by weight of water were added as a binder, and the mixture was stirred and mixed for 60 minutes or 180 minutes in a planetary mixer to obtain a negative electrode mixture paste. These are referred to as negative electrode pastes 101 and 102, respectively.
- Tables 1 and 2 below show the average particle size data indicating the dispersibility of the mixture dispersion paste adjusted above. It also shows the permeability of the mixture when these mixture pastes were filtered through a 30-fim micropore filter.
- the mixture of the present invention in which the dispersion of the conductive agent is prepared in advance has a shorter dispersion time, that is, a smaller average particle size with less power compared to the mixture prepared for comparison, and It can be seen that a better dispersion state is obtained by suppressing the aggregation of the particles. Further, the residue on the filter when each comparative mixture paste was filtered was analyzed, and it was found that the paste was a carbon compound aggregate. Such a residue is not observed in the mixture paste of the present invention, and it can be seen that conductive agents such as acetylene black and graphite made of a carbon compound are well dispersed. Table 1 Example Positive electrode paste Conductive agent Shoge 1 1 1 1 1--t ⁇ ⁇ £ No.
- the positive electrode mixture paste prepared above was applied to both sides of a 30 m-thick aluminum foil current collector with a blade coater and dried.Then, it was compression-molded with a roller press and cut into a predetermined size. A positive electrode sheet was prepared. The thickness of the sheet after compression molding was set at 220 2m. Further, it was sufficiently dehydrated and dried with a far-infrared heater in a dry box (dry air having a dew point of 150 to 170 ° C) to prepare a positive electrode sheet.
- the prepared negative electrode mixture paste was applied to a 20 / im copper foil current collector, and a negative electrode sheet was prepared in the same manner as in the preparation of the positive electrode sheet.
- the mixture paste was adjusted by mixing and mixing for 60 minutes in the same manner as the comparative mixture paste 101. As a result, a negative electrode sheet was prepared.
- the positive electrode sheet, the microporous polypropylene film separator 1, the negative electrode sheet, and the separator were laminated in this order, and spirally wound.
- the wound body was housed in a nickel-plated iron bottomed cylindrical battery can also serving as a negative electrode terminal. Further 1 mole / liter of E Ji Ren carbonate L i PF 6 as an electrolytic solution and 1, 2 - equal volumes mixture of dimethyl Tokishetan was injected into the battery can.
- a cylindrical battery was fabricated by caulking the battery lid with the positive terminal through a gasket.
- Table 3 shows the combinations of cathode and anode pastes and the capacity ratios in these batteries.
- a mixture prepared by preparing in advance a dispersion of a conductive agent consisting of carbon compounds Cylindrical batteries using either one or both of the positive and negative sheets show lower capacity than the combination without either.
- Negative electrode materials (1) to (10) were used as the negative electrode material and the positive electrode active material, respectively.
- Negative electrode materials (1) to (10) were used as the negative electrode material and the positive electrode active material, respectively.
- Negative electrode material (1) (7) SnS i 0 6 A l 0 3 B 0 3 P 0 2 O 3 6 acetylene black (electro-chemical (center particle Sa I's 5 ⁇ m) 200 parts by weight, as a conductive agent Denka Black Co., Ltd.) 10 Heavy Children, Graphite (Lonza Japan K
- the negative electrode materials 8 and 9 using the negative electrode materials 8 and 9 and adding 0.5 parts by weight of lithium hydroxide as a pH adjuster together with the negative electrode material in advance, and adjusting the mixture mixture paste as above to obtain a negative electrode paste 108 and 109, and the case where 3 parts by weight of lithium hydroxide is added using the negative electrode material 8 is referred to as the negative electrode paste 208. Further, 1 part by weight of sodium carbonate as a pH adjusting agent was added to the negative electrode paste 8, and the mixture was further stirred and mixed for 5 minutes to obtain a negative electrode paste 308.
- the negative electrode paste was kept at a constant temperature in a thermostatic water bath, and after a predetermined time, each was coated on both sides of a 20 / m-thick foil collector using a blade coater and dried. Thereafter, it was compression-molded by a roller press and cut into a predetermined size to form a strip-shaped negative electrode sheet.
- the thickness of the sheet after compression molding was 90 jwm. Further, it was fully dehydrated and dried with a far-infrared heater in a dry box (dry air with a dew point of 150 ⁇ 70 ° C) to prepare a negative electrode sheet.
- Positive active material (1) 200 parts by weight of LiCo02 (center particle size 5 // m), 10 parts by weight of acetylene black as a conductive agent (Denka Black manufactured by Electrochemical Co., Ltd.) 8 parts by weight of an aqueous dispersion (solid content: 50% by weight) of a copolymer of 2-ethylhexyl acrylate, acrylic acid and acrylonitrile as a binder, and 2% by weight carboxymethyl cellulose aqueous solution as a dispersant 6 0 parts was preliminarily mixed in a planetary mixer for 5 minutes, 50 parts by weight of water was added, and the mixture was further stirred and mixed for 20 minutes to obtain a positive electrode mixture dispersed paste.
- This mixture paste is referred to as “positive electrode paste 1”.
- the mixture-dispersed pastes prepared using the positive electrode active materials (2) and (3) are referred to as positive electrode paste 2 and positive electrode paste 3, respectively.
- the prepared positive electrode mixture pastes 1, 2, and 3 were each applied to a 30-jum aluminum foil current collector, and positive electrode sheets 1, 2, and 3 were formed in the same manner as the negative electrode sheet.
- the negative electrode sheet, the microporous polypropylene film separator, the positive electrode sheet and the separator were laminated in this order, and the resultant was spirally wound.
- the wound body was housed in an iron bottomed cylindrical battery can provided with nickel plating also serving as a negative electrode terminal. Further ethylene Kabone Bok and 1 1 mole Z 1 of L i PF 6 as an electrolytic solution was injected equal volume mixture of 2-dimethyl Tokishetan into the battery can. A battery with a positive electrode terminal was swaged via a gasket to make a cylindrical battery.
- Tables 4 and 5 show the results of the cycle test when charging and discharging were performed at a current of 3.5 mA / m 2 per unit area of the electrode sheet and the combination of the anode and cathode sheets in these batteries.
- the value is the capacity storage after 300 cycles. Retention,
- Batteries manufactured using the negative electrode sheet using the negative electrode paste having a pH within the preferred range of the present invention used pastes with an excessively low pH. It has better cycle characteristics than batteries (batteries # 7, 8, and 12) or those using excessively high paste (battery # 10).
- a pH adjusting agent was previously added to adjust the pH of the mixture paste to a preferable range (negative electrode paste 108, 109Z battery numbers 9, 13), Immediately after adjusting the mixture paste, a pH adjuster was added to make a preferred range (negative electrode paste 3 08 Z battery No. 11) compared to those without a PH adjuster (battery Nos. 8 and 12) And excellent cycle characteristics.
- the positive electrode active material L i C o 0 2 8 7 parts by weight, were mixed at a ratio of graph eye preparative 9 parts by weight as a conductive agent, further N ip 0 1 LX 8 2 0 B ( manufactured by Nippon Zeon as a binder 3 parts by weight and 1 part of carboxymethylcellulose were added, and the slurry obtained by kneading with water as a medium was applied to both surfaces of a 20-thick aluminum foil support (current collector). After drying the applied material, it was compression-molded with a calender press to prepare a belt-shaped positive electrode sheet. Table 6 shows the thickness of the mixture on one side of the positive electrode sheet after compression molding.
- Nickel and aluminum lead plates were welded to the ends of the negative electrode sheet and positive electrode sheet, respectively, and then heat-treated at 150 ° C for 2 hours in dry air with a dew point of 40 ° C or less. did.
- the heat treatment was performed using a far infrared heater.
- the heat-treated positive electrode sheet 5 (indicated by reference numeral 5 in FIG. 1), a microporous polypropylene film separator (Celgard 240) 3, a heat-treated negative electrode sheet 4 and a separator 3 are stacked in this order. I browsed it and wound it in a spiral.
- the wound body was housed in a nickel-plated iron bottomed cylindrical battery can 2 also serving as a negative electrode terminal. Further, 1 mo 1 Norritol ⁇ Li PF 6 (a mixture of ethylene carbonate and getyl carbonate in a ratio of 2 to 8 by weight) was injected into the battery can as an electrolyte.
- the battery lid 8 having the positive electrode terminal was caulked via the gasket 1 to produce a cylindrical battery.
- the positive electrode terminal 8 was connected to the positive electrode sheet 5 and the battery can 2 was connected to the negative electrode sheet 4 by a lead terminal in advance.
- Figure 1 shows a cross section of a cylindrical battery. 7 is a safety valve.
- the completed battery was charged to 4.2 V at a current density of 1 mA / cm 2 and then discharged repeatedly to 2.7 V to perform a charge / discharge cycle test.
- the discharge capacity was 60% of the initial value.
- the number of cycles before reaching is defined as the charge / discharge cycle life.
- the internal resistance of the battery at 1 kHz was also measured. The results are shown in Table 6. Table 6
- the non-aqueous secondary battery of the present invention and the method for producing the same, it is possible to stably obtain excellent battery performance such as charge-discharge cyclability.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/839,239 US6019802A (en) | 1994-10-27 | 1995-10-26 | Nonaqueous secondary battery and process for producing the same using a dispersion aid |
JP51444796A JP3726163B2 (ja) | 1994-10-27 | 1995-10-26 | 非水二次電池とその製造方法 |
EP95935575A EP0789412B1 (en) | 1994-10-27 | 1995-10-26 | Nonaqueous secondary cell and its manufacturing method |
AU37541/95A AU3754195A (en) | 1994-10-27 | 1995-10-26 | Nonaqueous secondary cell and its manufacturing method |
DE69514678T DE69514678T2 (de) | 1994-10-27 | 1995-10-26 | Nichtwässrige sekundärzelle und deren herstellungsverfahren |
CA002203802A CA2203802A1 (en) | 1994-10-27 | 1995-10-26 | Nonaqueous secondary battery and process for producing the same |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26379494 | 1994-10-27 | ||
JP6/263794 | 1994-10-27 | ||
JP29363594 | 1994-11-04 | ||
JP6/293635 | 1994-11-04 | ||
JP7/75232 | 1995-03-31 | ||
JP7523295 | 1995-03-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996013873A1 true WO1996013873A1 (fr) | 1996-05-09 |
Family
ID=27301741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1995/002205 WO1996013873A1 (fr) | 1994-10-27 | 1995-10-26 | Cellule secondaire non aqueuse et son procede de fabrication |
Country Status (7)
Country | Link |
---|---|
US (1) | US6019802A (ja) |
EP (1) | EP0789412B1 (ja) |
JP (1) | JP3726163B2 (ja) |
CN (1) | CN1085898C (ja) |
AU (1) | AU3754195A (ja) |
DE (1) | DE69514678T2 (ja) |
WO (1) | WO1996013873A1 (ja) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09512662A (ja) * | 1995-03-01 | 1997-12-16 | ウィルソン グレイトバッチ リミテッド | 電気化学電池に使用する水性混合電極材料及び製造方法 |
JPH10144302A (ja) * | 1996-11-06 | 1998-05-29 | Japan Storage Battery Co Ltd | 非水電解質電池用電極の製造方法及びその電極を用いた非水電解質電池 |
EP0867955A1 (en) * | 1997-03-26 | 1998-09-30 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
EP0986118A1 (en) * | 1997-05-27 | 2000-03-15 | TDK Corporation | Method of producing electrode for non-aqueous electrolytic cells |
EP0986115A1 (en) * | 1997-05-27 | 2000-03-15 | TDK Corporation | Electrode for non-aqueous electrolytic cells |
JP2002134101A (ja) * | 2000-10-20 | 2002-05-10 | Matsushita Electric Ind Co Ltd | リチウム2次電池用正極板の製造方法 |
JP2002134113A (ja) * | 2000-10-30 | 2002-05-10 | Matsushita Electric Ind Co Ltd | 非水系二次電池 |
JP2005293942A (ja) * | 2004-03-31 | 2005-10-20 | Nec Corp | 二次電池用負極の製造方法 |
JP2006100222A (ja) * | 2004-09-30 | 2006-04-13 | Sanyo Electric Co Ltd | リチウム二次電池用負極及びその製造方法 |
JP2006302617A (ja) * | 2005-04-19 | 2006-11-02 | Nissan Motor Co Ltd | 二次電池用電極の製造方法 |
JP2009064564A (ja) * | 2007-09-04 | 2009-03-26 | Sanyo Electric Co Ltd | 非水電解質電池用正極の製造方法、それに用いられるスラリー及び非水電解質電池 |
US7883798B2 (en) | 2001-07-19 | 2011-02-08 | Samsung Sdi Co., Ltd. | Active material for battery and method of preparing the same |
JP2011060612A (ja) * | 2009-09-10 | 2011-03-24 | Toyota Motor Corp | 二次電池および該電池の製造方法 |
JP2011249339A (ja) * | 2011-07-27 | 2011-12-08 | Nec Corp | リチウム二次電池及びその負極の製造方法 |
JP2014071947A (ja) * | 2012-09-27 | 2014-04-21 | Gs Yuasa Corp | 非水電解液二次電池及びその製造方法 |
JP2014096390A (ja) * | 2009-10-22 | 2014-05-22 | Nippon Electric Glass Co Ltd | 蓄電デバイス用負極活物質及びその製造方法 |
JP2020038191A (ja) * | 2018-08-31 | 2020-03-12 | Jfeスチール株式会社 | 有機−無機複合皮膜を有する金属材料における皮膜中の有機成分の分析方法、および、有機−無機複合皮膜を有する金属材料の製造方法 |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09306497A (ja) * | 1996-05-20 | 1997-11-28 | Japan Storage Battery Co Ltd | 鉛蓄電池用負極板 |
AU7451998A (en) * | 1997-05-27 | 1998-12-30 | Tdk Corporation | Electrode for non-aqueous electrolytic cells |
KR19990025888A (ko) * | 1997-09-19 | 1999-04-06 | 손욱 | 리튬 계열 이차 전지용 극판의 제조 방법 |
JP3547953B2 (ja) * | 1997-09-30 | 2004-07-28 | 三洋電機株式会社 | 円筒型非水電解液二次電池の製造方法 |
KR100263153B1 (ko) * | 1998-01-22 | 2000-08-01 | 김순택 | 리튬이온2차전지의전극결합제와활물질슬러리제조방법 |
JP3573964B2 (ja) * | 1998-06-17 | 2004-10-06 | 三洋電機株式会社 | アルカリ電池用水素吸蔵合金電極及びアルカリ蓄電池用水素吸蔵合金電極の製造方法 |
FR2781932B1 (fr) * | 1998-07-10 | 2000-09-01 | Giat Ind Sa | Electrolyte solide polymere et ses procedes de preparation |
JP3526223B2 (ja) | 1998-09-17 | 2004-05-10 | 日本碍子株式会社 | リチウム二次電池 |
JP3541723B2 (ja) * | 1999-04-28 | 2004-07-14 | 新神戸電機株式会社 | 円筒形リチウムイオン電池 |
US6589694B1 (en) * | 1999-05-14 | 2003-07-08 | Mitsubishi Cable Industries, Ltd. | Positive electrode active material, positive electrode active material composition and lithium ion secondary battery |
JP4453122B2 (ja) * | 1999-06-23 | 2010-04-21 | パナソニック株式会社 | 非水電解質二次電池 |
JP4938919B2 (ja) | 2000-01-14 | 2012-05-23 | ソニー株式会社 | 二次電池 |
JP3580213B2 (ja) * | 2000-02-28 | 2004-10-20 | 松下電器産業株式会社 | 円筒形電池用封口板 |
JP4106644B2 (ja) * | 2000-04-04 | 2008-06-25 | ソニー株式会社 | 電池およびその製造方法 |
TW508861B (en) * | 2000-08-08 | 2002-11-01 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and positive electrode for the same |
US6803149B2 (en) * | 2000-12-04 | 2004-10-12 | Shin-Kobe Electric Machinery Co., Ltd. | Non-aqueous electrolytic solution secondary battery |
WO2002054526A1 (fr) * | 2000-12-27 | 2002-07-11 | Mitsubishi Chemical Corporation | Element secondaire au lithium |
JP3871518B2 (ja) * | 2001-03-13 | 2007-01-24 | 松下電器産業株式会社 | アルカリ蓄電池用正極活物質、正極および正極の製造法 |
DE10125616A1 (de) | 2001-05-25 | 2002-12-05 | Microbatterie Gmbh | Verfahren zur Herstellung von Elektrodenfolien für galvanische Elemente |
JP3942386B2 (ja) * | 2001-07-04 | 2007-07-11 | 松下電器産業株式会社 | アルカリ蓄電池用正極 |
CN100438142C (zh) * | 2001-09-26 | 2008-11-26 | 三星Sdi株式会社 | 电极材料、制备电极材料方法、电极和包括该电极的电池 |
US6998192B1 (en) | 2002-08-29 | 2006-02-14 | Quallion Llc | Negative electrode for a nonaqueous battery |
US6852449B2 (en) * | 2002-08-29 | 2005-02-08 | Quallion Llc | Negative electrode including a carbonaceous material for a nonaqueous battery |
JP4140425B2 (ja) * | 2003-04-10 | 2008-08-27 | ソニー株式会社 | 二次電池 |
CN100418250C (zh) * | 2004-07-19 | 2008-09-10 | 肇庆市风华锂电池有限公司 | 二次电池成品极片的制备工艺及制备装置 |
CN100483837C (zh) * | 2004-07-28 | 2009-04-29 | 比亚迪股份有限公司 | 大倍率锂离子二次电池 |
US7174207B2 (en) * | 2004-09-23 | 2007-02-06 | Quallion Llc | Implantable defibrillator having reduced battery volume |
KR100917733B1 (ko) * | 2004-11-26 | 2009-09-15 | 파나소닉 주식회사 | 리튬 일차전지 및 그 제조법 |
JP4911909B2 (ja) * | 2005-03-29 | 2012-04-04 | 三洋電機株式会社 | リチウム二次電池用電極の製造方法 |
KR100709870B1 (ko) * | 2005-04-27 | 2007-04-20 | 삼성에스디아이 주식회사 | 이차 전지 및 그 형성 방법 |
JP5603011B2 (ja) * | 2005-11-17 | 2014-10-08 | インフィニット パワー ソリューションズ, インコーポレイテッド | 電気化学的装置及び該装置の製造方法 |
CN101207193B (zh) * | 2006-12-21 | 2010-11-17 | 比亚迪股份有限公司 | 一种电极浆料的制备方法 |
TWI332284B (en) * | 2006-12-29 | 2010-10-21 | Ind Tech Res Inst | A battery electrode paste composition containing modified maleimides |
JP5482173B2 (ja) | 2008-12-22 | 2014-04-23 | 住友化学株式会社 | 電極合剤、電極および非水電解質二次電池 |
JP5493516B2 (ja) * | 2009-07-06 | 2014-05-14 | ソニー株式会社 | 電極及びそれを有する電池 |
JP5609283B2 (ja) * | 2010-06-08 | 2014-10-22 | セントラル硝子株式会社 | リチウムイオン電池用電解液の製造方法およびそれを用いたリチウムイオン電池 |
JP2014505980A (ja) * | 2011-01-13 | 2014-03-06 | ビーエーエスエフ ソシエタス・ヨーロピア | リチウム−硫黄電池用の電極を製造する方法 |
CN103370815B (zh) * | 2011-02-16 | 2016-04-13 | 松下知识产权经营株式会社 | 电池及电池的制造方法 |
FR2980042B1 (fr) | 2011-09-09 | 2014-10-24 | Commissariat Energie Atomique | Procede de fabrication d'une electrode et encre pour electrode |
DE112011105726T5 (de) | 2011-10-11 | 2014-07-10 | Toyota Jidosha Kabushiki Kaisha | Nichtwässrige Sekundärbatterie |
US10135062B2 (en) | 2011-12-21 | 2018-11-20 | Nexeon Limited | Fabrication and use of carbon-coated silicon monoxide for lithium-ion batteries |
KR101429009B1 (ko) * | 2012-04-26 | 2014-08-12 | 강윤규 | 이차전지 음극재 및 그 제조방법 |
GB2508218A (en) * | 2012-11-26 | 2014-05-28 | Leclanch S A | Electrode for the reduction of gassing in lithium titanate cells |
JP6354135B2 (ja) | 2013-02-12 | 2018-07-11 | 株式会社ジェイテクト | 蓄電材料の製造装置および製造方法 |
JP6321404B2 (ja) | 2014-02-26 | 2018-05-09 | 株式会社ジェイテクト | 蓄電材料の製造装置および製造方法 |
JP6291903B2 (ja) | 2014-02-26 | 2018-03-14 | 株式会社ジェイテクト | 混練装置 |
JP6239476B2 (ja) * | 2014-09-25 | 2017-11-29 | 信越化学工業株式会社 | 非水電解質二次電池用負極及び非水電解質二次電池 |
KR102019711B1 (ko) * | 2016-09-26 | 2019-11-14 | 주식회사 엘지화학 | 리튬-황 이차전지 양극용 아크릴 바인더 및 이의 용도 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01272049A (ja) * | 1988-04-21 | 1989-10-31 | Sony Corp | リチウム二次電池 |
JPH02158055A (ja) * | 1988-12-09 | 1990-06-18 | Matsushita Electric Ind Co Ltd | リチウム二次電池用の正極合剤の製造法 |
JPH04112455A (ja) * | 1990-08-31 | 1992-04-14 | Sanyo Electric Co Ltd | 二次電池 |
JPH05174818A (ja) * | 1991-12-18 | 1993-07-13 | Seiko Electronic Components Ltd | 非水電解質二次電池及びその負極活物質の製造方法 |
JPH05290833A (ja) * | 1992-04-10 | 1993-11-05 | Matsushita Electric Ind Co Ltd | 非水二次電池とその負極板の製造法 |
JPH07235295A (ja) * | 1994-02-21 | 1995-09-05 | Fuji Photo Film Co Ltd | 非水二次電池 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5446344A (en) * | 1977-09-20 | 1979-04-12 | Sanyo Electric Co | Method of producing positive plate for nonnaqueous battery |
JPS6041829B2 (ja) * | 1979-01-06 | 1985-09-19 | 株式会社日立製作所 | 非水電解液電池用正極の製造法 |
JPS60160563A (ja) * | 1984-01-18 | 1985-08-22 | Toshiba Battery Co Ltd | 非水電解液電池用正極の製造法 |
US5041199A (en) * | 1990-04-04 | 1991-08-20 | Gould Inc. | Process for producing electrodeposited electrodes for use in electrochemical cells |
JP2871077B2 (ja) * | 1990-11-20 | 1999-03-17 | 松下電器産業株式会社 | 非水電解質二次電池用負極の製造法 |
JPH0529022A (ja) * | 1991-07-19 | 1993-02-05 | Honda Motor Co Ltd | リチウム二次電池用正極の製造方法 |
EP0627776B1 (en) * | 1993-05-14 | 1997-08-13 | Sharp Kabushiki Kaisha | Lithium secondary battery |
DE4342039A1 (de) * | 1993-12-09 | 1995-06-14 | Varta Batterie | Elektrochemisches Sekundärelement |
US5683834A (en) * | 1994-09-07 | 1997-11-04 | Fuji Photo Film Co., Ltd. | Nonaqueous secondary battery |
JP3756232B2 (ja) * | 1996-01-17 | 2006-03-15 | 宇部興産株式会社 | 非水電解質二次電池 |
-
1995
- 1995-10-26 WO PCT/JP1995/002205 patent/WO1996013873A1/ja active IP Right Grant
- 1995-10-26 AU AU37541/95A patent/AU3754195A/en not_active Abandoned
- 1995-10-26 JP JP51444796A patent/JP3726163B2/ja not_active Expired - Fee Related
- 1995-10-26 DE DE69514678T patent/DE69514678T2/de not_active Expired - Lifetime
- 1995-10-26 CN CN95196625A patent/CN1085898C/zh not_active Expired - Lifetime
- 1995-10-26 EP EP95935575A patent/EP0789412B1/en not_active Expired - Lifetime
- 1995-10-26 US US08/839,239 patent/US6019802A/en not_active Expired - Lifetime
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01272049A (ja) * | 1988-04-21 | 1989-10-31 | Sony Corp | リチウム二次電池 |
JPH02158055A (ja) * | 1988-12-09 | 1990-06-18 | Matsushita Electric Ind Co Ltd | リチウム二次電池用の正極合剤の製造法 |
JPH04112455A (ja) * | 1990-08-31 | 1992-04-14 | Sanyo Electric Co Ltd | 二次電池 |
JPH05174818A (ja) * | 1991-12-18 | 1993-07-13 | Seiko Electronic Components Ltd | 非水電解質二次電池及びその負極活物質の製造方法 |
JPH05290833A (ja) * | 1992-04-10 | 1993-11-05 | Matsushita Electric Ind Co Ltd | 非水二次電池とその負極板の製造法 |
JPH07235295A (ja) * | 1994-02-21 | 1995-09-05 | Fuji Photo Film Co Ltd | 非水二次電池 |
Non-Patent Citations (1)
Title |
---|
See also references of EP0789412A4 * |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09512662A (ja) * | 1995-03-01 | 1997-12-16 | ウィルソン グレイトバッチ リミテッド | 電気化学電池に使用する水性混合電極材料及び製造方法 |
JPH10144302A (ja) * | 1996-11-06 | 1998-05-29 | Japan Storage Battery Co Ltd | 非水電解質電池用電極の製造方法及びその電極を用いた非水電解質電池 |
EP0867955A1 (en) * | 1997-03-26 | 1998-09-30 | Seiko Instruments Inc. | Non-aqueous electrolyte secondary battery |
EP0986118A1 (en) * | 1997-05-27 | 2000-03-15 | TDK Corporation | Method of producing electrode for non-aqueous electrolytic cells |
EP0986115A1 (en) * | 1997-05-27 | 2000-03-15 | TDK Corporation | Electrode for non-aqueous electrolytic cells |
EP0986118A4 (en) * | 1997-05-27 | 2001-04-11 | Tdk Corp | METHOD FOR PRODUCING AN ELECTRODE FOR NON-AQUEOUS ELECTROLYTIC CELLS |
US6497979B1 (en) | 1997-05-27 | 2002-12-24 | Tdk Corporation | Method of producing electrode for non-aqueous electrolytic cells including a narrow-gap dispersing process |
EP0986115A4 (en) * | 1997-05-27 | 2005-03-02 | Tdk Corp | ELECTRODE FOR NONAQUEOUS ELECTROLYTIC CELLS |
JP2002134101A (ja) * | 2000-10-20 | 2002-05-10 | Matsushita Electric Ind Co Ltd | リチウム2次電池用正極板の製造方法 |
JP2002134113A (ja) * | 2000-10-30 | 2002-05-10 | Matsushita Electric Ind Co Ltd | 非水系二次電池 |
US7883798B2 (en) | 2001-07-19 | 2011-02-08 | Samsung Sdi Co., Ltd. | Active material for battery and method of preparing the same |
JP2005293942A (ja) * | 2004-03-31 | 2005-10-20 | Nec Corp | 二次電池用負極の製造方法 |
JP2006100222A (ja) * | 2004-09-30 | 2006-04-13 | Sanyo Electric Co Ltd | リチウム二次電池用負極及びその製造方法 |
JP2006302617A (ja) * | 2005-04-19 | 2006-11-02 | Nissan Motor Co Ltd | 二次電池用電極の製造方法 |
JP2009064564A (ja) * | 2007-09-04 | 2009-03-26 | Sanyo Electric Co Ltd | 非水電解質電池用正極の製造方法、それに用いられるスラリー及び非水電解質電池 |
JP2011060612A (ja) * | 2009-09-10 | 2011-03-24 | Toyota Motor Corp | 二次電池および該電池の製造方法 |
JP2014096390A (ja) * | 2009-10-22 | 2014-05-22 | Nippon Electric Glass Co Ltd | 蓄電デバイス用負極活物質及びその製造方法 |
JP2014130826A (ja) * | 2009-10-22 | 2014-07-10 | Nippon Electric Glass Co Ltd | 蓄電デバイス用負極活物質及びその製造方法 |
JP2011249339A (ja) * | 2011-07-27 | 2011-12-08 | Nec Corp | リチウム二次電池及びその負極の製造方法 |
JP2014071947A (ja) * | 2012-09-27 | 2014-04-21 | Gs Yuasa Corp | 非水電解液二次電池及びその製造方法 |
JP2020038191A (ja) * | 2018-08-31 | 2020-03-12 | Jfeスチール株式会社 | 有機−無機複合皮膜を有する金属材料における皮膜中の有機成分の分析方法、および、有機−無機複合皮膜を有する金属材料の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JP3726163B2 (ja) | 2005-12-14 |
EP0789412B1 (en) | 2000-01-19 |
EP0789412A4 (en) | 1998-04-01 |
US6019802A (en) | 2000-02-01 |
CN1085898C (zh) | 2002-05-29 |
DE69514678D1 (de) | 2000-02-24 |
AU3754195A (en) | 1996-05-23 |
DE69514678T2 (de) | 2000-06-15 |
EP0789412A1 (en) | 1997-08-13 |
CN1168742A (zh) | 1997-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO1996013873A1 (fr) | Cellule secondaire non aqueuse et son procede de fabrication | |
EP3331066B1 (en) | Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material | |
EP1291941B1 (en) | Active material for battery and method of preparing the same | |
JP4329730B2 (ja) | 非水二次電池とその製造方法 | |
JP2903469B1 (ja) | リチウムイオン電池用陽極材料の製造方法 | |
JP2008147068A (ja) | 非水電解液二次電池用リチウム複合酸化物 | |
JP3498380B2 (ja) | 非水二次電池 | |
JPH09180758A (ja) | 非水二次電池 | |
JPH11185753A (ja) | 非水電解質リチウム二次電池 | |
JP3555213B2 (ja) | 非水二次電池 | |
JPH09231963A (ja) | 非水二次電池 | |
JP4235702B2 (ja) | 正極活物質とその製造方法とこれを用いた非水電解質二次電池 | |
JP4038826B2 (ja) | 非水電解液二次電池および製造法 | |
JP3819940B2 (ja) | 非水電解質二次電池 | |
JP2006318926A (ja) | 正極活物質及び非水電解質二次電池 | |
JP7040832B1 (ja) | リチウムイオン二次電池用負極活物質、その製造方法、及びリチウムイオン二次電池用負極電極 | |
JP3503688B2 (ja) | リチウム二次電池 | |
KR20090108570A (ko) | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지 | |
JPH08130035A (ja) | 非水二次電池 | |
JP4285407B2 (ja) | リチウム二次電池用非水電解液及び非水電解液二次電池 | |
WO2023166869A1 (ja) | リチウムイオン二次電池用負極活物質、その製造方法、及びリチウムイオン二次電池用負極電極 | |
KR20150078068A (ko) | 리튬 이차전지용 음극 활물질의 제조방법 및 리튬 이차전지 | |
JP7163624B2 (ja) | リチウムイオン二次電池用正極活物質及びその製造方法、並びにその正極活物質を用いたリチウムイオン二次電池 | |
WO2020080211A1 (ja) | リチウム二次電池用正極活物質、その製造方法及びリチウム二次電池 | |
JP2005317447A (ja) | 電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 95196625.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AU CA CN FI JP KR SG US VN |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 08839239 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2203802 Country of ref document: CA Ref document number: 2203802 Country of ref document: CA Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1995935575 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1995935575 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1995935575 Country of ref document: EP |