WO2011037201A1 - 正極合剤、正極および非水電解質二次電池 - Google Patents
正極合剤、正極および非水電解質二次電池 Download PDFInfo
- Publication number
- WO2011037201A1 WO2011037201A1 PCT/JP2010/066586 JP2010066586W WO2011037201A1 WO 2011037201 A1 WO2011037201 A1 WO 2011037201A1 JP 2010066586 W JP2010066586 W JP 2010066586W WO 2011037201 A1 WO2011037201 A1 WO 2011037201A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- active material
- weight
- material powder
- electrode active
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of 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
- H01M4/36—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
- H01M4/62—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode mixture, a positive electrode, and a nonaqueous electrolyte secondary battery.
- the positive electrode mixture includes a positive electrode active material powder, a conductive agent, a binder, and a solvent.
- the positive electrode is manufactured by applying a positive electrode mixture to a current collector to obtain a coated current collector, and drying the coated current collector.
- the positive electrode is used for a non-aqueous electrolyte secondary battery and the like.
- non-aqueous electrolyte secondary batteries typical lithium secondary batteries have already been put into practical use as small power sources for mobile phones and laptop computers, and also as medium and large power sources for automobiles and power storage applications. Application is being attempted.
- Patent Document 1 discloses a positive electrode active material powder having an average particle diameter of 9.1 ⁇ m to 20.5 ⁇ m.
- a non-aqueous electrolyte secondary battery using a positive electrode obtained by applying a positive electrode mixture having the powder to a current collector is required to have a high output at a high current rate because of its high internal resistance. It has not been suitable for uses such as automotive tools and power tools such as electric tools.
- Patent Document 2 discloses a positive electrode active material having an average particle size of 1.4 ⁇ m and 1.6 ⁇ m in its examples. The powder is described.
- An object of the present invention is to provide a positive electrode mixture and a positive electrode that provide a nonaqueous electrolyte secondary battery capable of exhibiting higher output at a high current rate.
- the inventors of the present invention focused on the point that the fine powder such as the positive electrode active material powder in Patent Document 2 has a weak aggregation between the particles, so that it is difficult to promote the mixing with the conductive agent.
- the present inventors have found a positive electrode mixture that gives a positive electrode of a non-aqueous electrolyte secondary battery that exhibits higher output even if the particles constituting the positive electrode active material powder are fine particles. It has been found that the nonaqueous electrolyte secondary battery used can exhibit higher output at a higher current rate.
- a positive electrode mixture containing a positive electrode active material powder, a conductive agent, a binder and a solvent The positive electrode active material powder is composed of particles having an average particle size of 0.05 ⁇ m or more and 1 ⁇ m or less, The positive electrode active material powder has a tap density of 0.8 to 3.0 g / cm 3 , The amount of the conductive agent with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 20 parts by weight, The amount of the binder with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 10 parts by weight, The amount of the solvent with respect to 100 parts by weight of the positive electrode active material powder is 10 to 120 parts by weight, and The viscosity is 1000-25000 mPa ⁇ s.
- Positive electrode mixture ⁇ 2> The positive electrode mixture according to ⁇ 1>, wherein the weight ratio of the positive electrode active material powder to the total weight of the positive electrode active material powder, the conductive agent and the binder is 77 to 99% by weight.
- ⁇ 4> The positive electrode mixture according to any one of ⁇ 1> to ⁇ 3>, wherein the positive electrode active material powder is composed of a lithium composite metal oxide containing Ni and Mn.
- the positive electrode mixture of ⁇ 4>, wherein the lithium composite metal oxide is represented by the following formula (A).
- ⁇ 8> The positive electrode mixture according to any one of ⁇ 1> to ⁇ 7>, wherein the conductive material has a bulk density of 0.01 to 1.3 g / cm 3 .
- ⁇ 9> The positive electrode mixture according to any one of ⁇ 1> to ⁇ 8>, wherein the binder has a glass transition temperature of ⁇ 30 ° C. to ⁇ 40 ° C.
- ⁇ 10> The positive electrode mixture according to any one of ⁇ 1> to ⁇ 9>, wherein the binder is composed of polyvinylidene fluoride.
- the weight ratio of the binder to the total weight of the binder and the solvent is 1 to 20% by weight.
- ⁇ 12> The positive electrode mixture according to any one of ⁇ 1> to ⁇ 11>, wherein the solvent has a density of 0.935 to 1.200 g / cm 3 .
- a positive electrode mixture according to any one of ⁇ 1> to ⁇ 12> is applied to a current collector to obtain a coated current collector, and the solvent is removed from the coated current collector.
- ⁇ 14> A nonaqueous electrolyte secondary battery having the positive electrode of ⁇ 13>.
- the present invention it is possible to obtain a nonaqueous electrolyte secondary battery that exhibits higher output at a higher current rate than a conventional lithium secondary battery.
- the secondary battery is used in applications that require high output at a high current rate, that is, applications that require a large current, such as driving motors such as automobiles and electric tools, and applications that require rapid charge / discharge.
- the present invention is extremely useful industrially.
- the positive electrode mixture of the present invention contains a positive electrode active material powder, a conductive agent, a binder and a solvent.
- the positive electrode active material powder is composed of particles having an average particle size of 0.05 ⁇ m or more and 1 ⁇ m or less.
- the positive electrode active material powder has a tap density of 0.8 to 3.0 g / cm 3 .
- the amount of the conductive agent with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 20 parts by weight.
- the amount of the binder with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 10 parts by weight.
- the amount of the solvent with respect to 100 parts by weight of the positive electrode active material powder is 10 to 120 parts by weight.
- the viscosity of the positive electrode mixture is 1000 to 25000 mPa ⁇ s.
- the positive electrode mixture of the present invention is suitably used for a nonaqueous electrolyte secondary battery.
- Viscosity is determined by measuring a measurement object at a temperature of 25 ° C. and a rotation speed of 10 rpm using a rotational viscometer.
- An example of the rotational viscometer is a corn / plate viscometer manufactured by Brookfield.
- the positive electrode active material powder is usually composed of primary particles and aggregated particles of primary particles.
- the average particle diameter of the particles constituting the positive electrode active material powder is 0.05 ⁇ m or more, or 0.10 ⁇ m or more, and is 1 ⁇ m or less, 0.7 ⁇ m or less, 0.5 ⁇ m or less.
- the average particle diameter is a value of D50 determined by laser diffraction particle size distribution measurement.
- As an apparatus for laser diffraction particle size distribution measurement there is a laser diffraction particle size distribution measurement apparatus (model: Mastersizer 2000) manufactured by Malvern. If the average particle size of the particles constituting the positive electrode active material powder is too small, there may be a problem in terms of reactivity with the electrolytic solution. Further, if the average particle size is too large, it tends to be difficult to obtain a high output battery.
- the tap density of the positive electrode active material powder is 0.8 g / cm 3 or more, 1.0 g / cm 3 or more, or 1.5 g / cm 3 or more, and 3.0 g / cm 3 or less.
- the tap density is calculated by adding the positive electrode active material powder of a predetermined weight to the graduated cylinder, reading the total volume of particles and inter-particle voids when tapping them 200 times, and dividing the positive electrode active material weight by the total volume. To be determined.
- the tap density can also be determined using a tap denser KYT4000 manufactured by Seishin Corporation.
- the tap density of the positive electrode active material powder When the tap density of the positive electrode active material powder is too small, the amount of the positive electrode active material per volume of the positive electrode to be obtained decreases, and the energy density of the positive electrode tends to decrease.
- the upper limit of the tap density is 3.0 g / cm 3 .
- the positive electrode mixture of the present invention contains the positive electrode active material powder, the conductive agent, the binder and the solvent in a specific amount ratio, and is 1000 Pa ⁇ s or more, 3000 mPa ⁇ s or more, 5000 mPa ⁇ s or more, or 8000 mPa ⁇ s or more. 25000 mPa ⁇ s or less, or 20000 mPa ⁇ s or less.
- the positive electrode obtained by using the positive electrode mixture of the present invention is used in a non-aqueous electrolyte secondary battery, it is possible to obtain a non-aqueous electrolyte secondary battery that exhibits higher output at a high current rate, that is, a battery that is superior in output characteristics. it can.
- the amount of the conductive agent with respect to 100 parts by weight of the positive electrode active material powder is 0.5 parts by weight or more, 1 part by weight or more, or 3 parts by weight or more, and is 20 parts by weight or less, 15 parts by weight or less, or 20 parts by weight or less. It is.
- amount of conductive agent When there is too little quantity of a electrically conductive agent, it exists in the tendency for the electroconductivity of the positive electrode obtained to fall. Moreover, when there is too much quantity of a electrically conductive agent, there exists a tendency for the amount of positive electrode active materials per weight of a positive electrode to decrease, and for the energy density of a positive electrode to fall.
- the amount of the binder with respect to 100 parts by weight of the positive electrode active material powder is 0.5 parts by weight or more, parts by weight or more, 1 part by weight or more, or 3 parts by weight or more, and 10 parts by weight or less. If the amount of the binder is too small, it is not preferable in terms of the adhesive force of the positive electrode mixture to the current collector. Moreover, when there is too much quantity of a binder, it exists in the tendency for the amount of positive electrode active materials per weight of a positive electrode to decrease, and for the energy density of a positive electrode to fall.
- the amount of the solvent with respect to 100 parts by weight of the positive electrode active material powder is 10 parts by weight or more, or 20 parts by weight or more, and is 120 parts by weight or 100 parts by weight or less.
- amount of the solvent is too small, coating on the current collector tends to be difficult.
- there is too much quantity of a solvent it exists in the tendency for the drying after coating to become difficult.
- the weight ratio of the positive electrode active material powder to the total weight of the positive electrode active material powder weight, the conductive agent weight, and the binder weight is 77% by weight, 80% by weight, or 90% by weight, and 99% by weight or less, or 95% by weight. The following is preferable. When the weight ratio of the positive electrode active material powder is within the above range, the discharge capacity and output characteristics of the obtained battery can be further improved.
- the positive electrode active material powder preferably has a BET specific surface area of 2 to 30 m 2 / g.
- BET specific surface area of the positive electrode active material powder is in the above range, the output characteristics of the obtained battery can be further enhanced, and the reactivity with the electrolyte solution described later can be further suppressed.
- the positive electrode active material powder in the present invention will be described more specifically. From the viewpoint of obtaining a non-aqueous electrolyte secondary battery that is environmentally friendly and has a high capacity, the positive electrode active material powder is preferably composed of a lithium composite metal oxide containing Ni and Mn.
- the lithium composite metal oxide is preferably represented by the following formula (A). Li ⁇ (Ni 1-(x + y + z) Mn x Fe y Co z ) O 2 (A) (Here, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x + y + z ⁇ 1, 0.5 ⁇ ⁇ ⁇ 1.5.)
- the lithium composite metal oxide is represented by the following formula (B). Li ⁇ (Ni 1-(x + y) Mn x Fe y ) O 2 (B) (Here, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ x + y ⁇ 1, 0.5 ⁇ ⁇ ⁇ 1.5.)
- the value of ⁇ is preferably 0.95 or more and 1.5 or less, more preferably 1.0 or more and 1.4 or less.
- the value of x + y is preferably 0.2 or more and 0.7 or less, and more preferably 0.3 or more and 0.6 or less.
- the value of y is preferably 0 or more and 0.2 or less, more preferably more than 0 and 0.2 or less, and still more preferably 0.005 or more and 0.1 or less.
- the amount (mol) of Mn in the lithium composite metal oxide is preferably larger than the amount (mol) of Ni. . That is, in the formula (A), it is preferable to satisfy the requirement of 1- (x + y + z) ⁇ x, and in the formula (B), it is preferable to satisfy the requirement of 1- (x + y) ⁇ x.
- the lithium composite metal oxide preferably has an ⁇ -NaFeO 2 type crystal structure, that is, a crystal structure belonging to the R-3m space group.
- the crystal structure of the lithium composite metal oxide can be identified from the powder X-ray diffraction pattern of the lithium composite metal oxide obtained by powder X-ray diffraction measurement using CuK ⁇ as a radiation source.
- a part of Li, Ni, Mn, Fe, or Co in the lithium composite metal oxide may be substituted with another element.
- B Al, Ga, In, Si, Ge, Sn, Mg, Sc, Y, Zr, Hf, Nb, Ta, Cr, Mo, W, Ru, Rh, Ir, Pd
- Examples include elements selected from Cu, Ag, Zn, and the like.
- a compound different from the lithium composite metal oxide may be attached to the surface of the particles constituting the lithium composite metal oxide.
- a compound containing at least one element selected from the group consisting of B, Al, Ga, In, Si, Ge, Sn, Mg and a transition metal element preferably B, Al, Mg, Ga
- Specific examples of the compound include oxides, hydroxides, oxyhydroxides, carbonates, nitrates, and organic acid salts of the elements, preferably oxides, hydroxides, and oxyhydroxides of the elements. It is done. These compounds may be mixed. Among these compounds, a particularly preferred compound is alumina. Moreover, you may heat after adhesion.
- the method for producing the positive electrode active material powder in the present invention will be specifically described.
- An example of a method for producing a powder of lithium composite metal oxide containing Ni and Mn will be described.
- the powder of lithium composite metal oxide containing Ni and Mn can be produced by holding and firing a mixture of a coprecipitate and a lithium compound at a temperature of 900 ° C. or lower.
- the coprecipitate is obtained by bringing an aqueous solution containing Ni, Mn, and Cl, and optionally Fe and Co (hereinafter, also referred to as “first aqueous solution”) into contact with an alkali.
- the coprecipitate may be obtained as a coprecipitate powder at the time of the contact, but is preferably obtained as a coprecipitate slurry.
- the shape of the coprecipitate obtained depends on the concentration of Ni, Mn, Fe, Co in the first aqueous solution and the form of the alkali (aqueous solution or solid) in contact with the first aqueous solution.
- an alkali about the 1st aqueous solution, an alkali, the contact method of 1st aqueous solution and this alkali, the mixing method of a lithium compound and a coprecipitate, the baking method of a mixture etc., the below-mentioned thing or method can be used. Mixing may be performed instead of coprecipitation.
- the positive electrode active material powder can be produced by firing a metal compound mixture.
- a compound containing a corresponding metal element is weighed so as to have a predetermined composition and mixed to obtain a metal compound mixture.
- positive electrode active material powder can be manufactured by baking a metal compound mixture.
- a method for producing a lithium composite metal oxide powder as a positive electrode active material powder used in the present invention a method having a step of obtaining the coprecipitate is more preferable because the desired powder characteristics can be easily obtained.
- the method for producing a lithium composite metal oxide powder preferably includes the following steps (1), (2) and (3).
- (2) A step of obtaining a coprecipitate from the coprecipitate slurry.
- (3) A step of obtaining a lithium composite metal oxide by holding and baking a mixture obtained by mixing the coprecipitate and the lithium compound at a temperature of 900 ° C. or lower.
- the first aqueous solution uses Ni, Mn, and, if necessary, respective chlorides as raw materials containing Fe, Co.
- Ni chloride, Mn chloride Accordingly, an aqueous solution obtained by dissolving Fe chloride and Co chloride in water is preferable.
- the Fe chloride is preferably a divalent Fe chloride.
- a first aqueous solution can be obtained.
- the first aqueous solution contains Ni, Mn, and optionally Fe and Co so as to have a predetermined molar ratio, that is, the molar ratio in the formula (A) or the formula (B).
- examples of the alkali include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (lithium carbonate), Na 2 CO 3 (sodium carbonate), K
- LiOH lithium hydroxide
- NaOH sodium hydroxide
- KOH potassium hydroxide
- Li 2 CO 3 lithium carbonate
- Na 2 CO 3 sodium carbonate
- K One or more compounds selected from the group consisting of 2 CO 3 (potassium carbonate) and (NH 4 ) 2 CO 3 (ammonium carbonate) may be mentioned, and these may be anhydrous or hydrated.
- these alkalis are preferably dissolved in water and used as an aqueous alkali solution.
- Aqueous ammonia can also be mentioned as an alkaline aqueous solution.
- the concentration of alkali in the alkaline aqueous solution is usually about 0.5 to 10M, preferably about 1 to 8M. From the viewpoint of production cost, it is preferable to use an anhydride and / or hydrate of NaOH or KOH as the alkali to be used. Two or more of the above alkalis may be used in combination.
- Examples of the contact method in step (1) include a method of adding and mixing an alkaline aqueous solution to the first aqueous solution, a method of adding and mixing the first aqueous solution to the alkaline aqueous solution, and the first aqueous solution and the alkaline aqueous solution in water.
- the method of adding and mixing can be mentioned. These mixing are preferably performed by stirring.
- the method of adding and mixing the first aqueous solution to the alkaline aqueous solution can be preferably used because it is easy to maintain the pH change. In this case, the pH of the mixed solution tends to decrease as the first aqueous solution is added to and mixed with the alkaline aqueous solution.
- the first aqueous solution may be added while adjusting the pH of the mixed solution to 9 or more, preferably 10 or more. It is preferable to bring the aqueous solutions into contact with each other while maintaining either one or both of the first aqueous solution and the alkaline aqueous solution at a temperature of 40 ° C. to 80 ° C., thereby obtaining a coprecipitate having a more uniform composition. be able to.
- step (1) a coprecipitate is generated as described above, and a coprecipitate slurry can be obtained.
- step (2) a coprecipitate is obtained from the coprecipitate slurry.
- step (2) may be performed by any method, but from the viewpoint of operability, a method by solid-liquid separation such as filtration is preferably used.
- the coprecipitate can also be obtained by a method in which the coprecipitate slurry is heated to volatilize the liquid, such as spray drying.
- the step (2) when the coprecipitate is obtained by solid-liquid separation, the step (2) is preferably the following step (2 ′).
- (2 ′) A step of solid-liquid separation of the coprecipitate slurry, and washing and drying the solid content to obtain a coprecipitate.
- step (2 ′) if alkali and Cl are excessively present in the solid content obtained after solid-liquid separation, this can be removed by washing.
- water it is preferable to use water as the washing liquid.
- step (2 ′) the solid content obtained by solid-liquid separation is washed and then dried to obtain a coprecipitate. Drying is usually performed by heat treatment. You may perform by ventilation drying, vacuum drying, etc. When drying is performed by heat treatment, the heat treatment temperature is usually about 50 to 300 ° C., preferably about 100 to 200 ° C.
- step (3) the mixture obtained by mixing the coprecipitate obtained above and the lithium compound is fired to obtain a lithium composite metal oxide powder, that is, a positive electrode active material powder.
- the lithium compound include one or more anhydrides and / or one or more hydrates selected from the group consisting of lithium hydroxide, lithium chloride, lithium nitrate, and lithium carbonate.
- the mixing may be either dry mixing or wet mixing, but from the viewpoint of simplicity, dry mixing is preferable.
- the mixing apparatus include a stirring mixer, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, and a ball mill.
- the holding temperature in the firing is an important factor from the viewpoint of adjusting the average particle size of the lithium composite metal oxide powder, that is, the positive electrode active material powder. Usually, the higher the holding temperature, the larger the average particle size tends to be.
- the holding temperature is preferably 650 ° C. or higher and 900 ° C. or lower.
- the holding time at the holding temperature is usually 0.1 hour to 20 hours, preferably 0.5 hour to 8 hours.
- the rate of temperature rise to the holding temperature is usually 50 ° C./hour to 400 ° C./hour, and the rate of temperature drop from the holding temperature to room temperature is usually 10 ° C./hour to 400 ° C./hour.
- the firing atmosphere include air, oxygen, nitrogen, argon, or a mixed gas thereof, and an air atmosphere is preferable.
- the mixture may contain a reaction accelerator.
- the reaction accelerator include chlorides such as NaCl, KCl and NH 4 Cl, fluorides such as LiF, NaF, KF and NH 4 F (ammonium fluoride), boric acid, preferably the chloride. More preferred is KCl.
- the reaction accelerator may be added and mixed when the coprecipitate and the lithium compound are mixed. The reaction accelerator may remain in the fired lithium composite metal oxide, or may be removed by washing of the fired lithium composite metal oxide or evaporation of the reaction accelerator itself.
- the lithium composite metal oxide powder obtained after the firing may be pulverized by a ball mill, a jet mill or the like. It may be possible to adjust the average particle size of the positive electrode active material powder by pulverization. The grinding and firing may be repeated twice or more. The positive electrode active material powder can be washed or classified as necessary. In this way, a positive electrode active material powder can be obtained.
- the conductive agent in the positive electrode mixture of the present invention is preferably a carbon material.
- the carbon material include graphite or non-graphite carbon material, and the carbon material may be composed of a single component or a mixed component.
- the bulk density of the conductive agent is preferably 0.01 to 1.3 g / cm 3 . The bulk density is determined by putting the conductive agent of the specified weight into the graduated cylinder, reading the total volume of particles and interparticle voids without tapping them, and dividing the conductive agent weight by the total volume. The Bulk density can also be determined using a multi tester MT-1001 manufactured by Seishin Corporation.
- graphite examples include graphite such as natural graphite and artificial graphite.
- non-graphitic carbon materials include carbon black and acetylene black.
- a fibrous carbon material may be used.
- Specific examples of the fibrous carbon material include graphitized carbon fiber and carbon nanotube.
- the carbon nanotube may be either a single wall or a multiwall.
- a commercially available material may be appropriately pulverized and used.
- the pulverization may be either dry or wet. Examples of dry pulverization include pulverization using a ball mill, rocking mill, and planetary ball mill. Examples of wet pulverization include pulverization using a ball mill and a day spa mat.
- thermoplastic resin is mentioned as a binder in the positive mix of this invention.
- the thermoplastic resin include polyvinylidene fluoride (hereinafter also referred to as PVdF), polytetrafluoroethylene (hereinafter also referred to as PTFE), tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride.
- fluororesins such as copolymers, propylene hexafluoride / vinylidene fluoride copolymers, tetrafluoroethylene / perfluorovinyl ether copolymers, and polyolefin resins such as polyethylene and polypropylene.
- the binder is preferably polyvinylidene fluoride. Two or more binders may be mixed.
- the binder is preferably a fluororesin and a polyolefin resin, whereby a positive electrode mixture having better binding properties with the current collector can be obtained.
- the binder can be used by dissolving or dispersing in a solvent described later.
- the binder in the positive electrode mixture of the present invention preferably has a glass transition temperature of ⁇ 30 to ⁇ 40 ° C.
- solvent in the positive electrode mixture of the present invention examples include ether solvents such as N, N-dimethylaminopropylamine, diethylenetriamine, N, N-dimethylformamide (hereinafter also referred to as DMF), and tetrahydrofuran.
- ether solvents such as N, N-dimethylaminopropylamine, diethylenetriamine, N, N-dimethylformamide (hereinafter also referred to as DMF), and tetrahydrofuran.
- ketone solvents such as methyl ethyl ketone
- ester solvents such as methyl acetate
- amide solvents such as dimethylacetamide and 1-methyl-2-pyrrolidone (hereinafter also referred to as NMP), dimethyl sulfoxide (hereinafter referred to as DMSO) and the like.
- NMP dimethyl sulfoxide
- DMSO dimethyl sulfoxide
- a solvent having a density of 0.935 to 1.200 g / cm 3 is preferable.
- solvents include diethylenetriamine (bp is 199-209 ° C., Fp is 94 ° C., d is 0.955), N, N-dimethylformamide (bp is 153 ° C., Fp is 57 ° C., d is 0.944).
- the electrode mixture of the present invention can be produced by mixing and kneading the following positive electrode active material powder, conductive agent, binder and solvent by the method described below:
- the positive electrode active material powder is composed of particles having an average particle diameter of 0.05 ⁇ m or more and 1 ⁇ m or less, and has a tap density of 0.8 to 3.0 g / cm 3 .
- the amount of the conductive agent with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 20 parts by weight
- the amount of the binder with respect to 100 parts by weight of the positive electrode active material powder is 0.5 to 10 parts by weight
- the amount of the solvent with respect to 100 parts by weight of the positive electrode active material powder is 10 to 120 parts by weight.
- the positive electrode active material powder, the conductive agent, the binder, and the solvent are preliminarily mixed with an ordinary mixer to obtain a premixed product.
- this premixed product is mixed and kneaded with a thin-film swirl type high-speed stirrer, whereby the positive electrode mixture of the present invention can be obtained.
- the thin-film swirl type high-speed stirrer includes a cylindrical container and a rotating wheel including a cylindrical part in which a plurality of holes that rotate in the vicinity of the inner surface of the container are formed.
- the premixed product is placed in a rotating wheel, and the premixed product moves to the inner wall of the container through a plurality of holes by centrifugal force generated by the rotation of the rotating wheel, and between the rotating wheel and the inner wall of the container.
- the premixed product is mixed and kneaded by the shearing force generated by the rotation of the rotating wheel.
- the positive electrode active material powder, the conductive agent, the binder, and the solvent may be mixed together, or the binder, the positive electrode active material powder, and the conductive agent may be mixed in order with the solvent. This order is not particularly limited. A mixture of the positive electrode active material powder and the conductive agent may be gradually added to the solvent. You may mix a solvent and a binder before premixing. As described above, the preliminary mixing may be batch mixing or sequential mixing.
- the weight ratio of the binder to the total weight of the binder and the solvent is preferably 1 to 20% by weight from the viewpoint of handling.
- the positive electrode mixture can be applied to a current collector to obtain a coated current collector, and the solvent can be removed from the coated current collector to produce a positive electrode.
- the removal of the solvent may be performed by drying.
- the current collector (hereinafter also referred to as a positive electrode current collector) include Al, Ni, stainless steel, and the like. Al is preferable because it is easy to process into a thin film and is inexpensive. After removing the solvent, the positive electrode may be pressed.
- Examples of the method of applying the positive electrode mixture to the current collector include a die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
- the nonaqueous electrolyte secondary battery has a positive electrode, a negative electrode, and an electrolyte, and further includes a separator as necessary.
- An example of the battery is a lithium secondary battery.
- an electrode group obtained by laminating or laminating and winding a separator, the above-described positive electrode, separator, and negative electrode is housed in a battery case such as a battery can, and then an electrolyte is contained in the case. It can manufacture by inject
- the shape of the electrode group for example, a shape in which the cross section when the electrode group is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, a rectangle with rounded corners, etc. Can be mentioned.
- examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
- the negative electrode only needs to be capable of doping and dedoping lithium ions at a potential lower than that of the positive electrode.
- the negative electrode material include carbon materials, chalcogen compounds (oxides, sulfides, and the like), nitrides, metals, and alloys that can be doped and dedoped with lithium ions at a lower potential than the positive electrode. Two or more negative electrode materials may be mixed and used.
- the negative electrode material is exemplified below.
- the carbon material include graphite such as natural graphite and artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fiber, and an organic polymer fired body.
- an oxide of silicon represented by the formula SiO x (where x is a positive real number) such as SiO 2 and SiO
- a formula TiO x such as TiO 2 and TiO (where x is x) Is a positive oxide of titanium, V 2 O 5 , VO 2, etc.
- VO x where x is a positive real number
- vanadium oxide Fe 3 O 4 , Fe 2 O 3 , FeO and the like FeO x (where x is a positive real number)
- Tin oxide tungsten oxide represented by general formula WO x (where x is a positive real number) such as WO 3
- the sulfide include titanium sulfides represented by the formula TiS x (where x is a positive real number) such as Ti 2 S 3 , TiS 2 , and TiS, V 3 S 4 , VS 2, VS and other formulas VS x (where x is a positive real number), vanadium sulfide, Fe 3 S 4 , FeS 2 , FeS and other formulas FeS x (where x is a positive real number) Iron sulfide, Mo 2 S 3 , MoS 2 and the like MoS x (where x is a positive real number) molybdenum sulfide, SnS 2, SnS and other formula SnS x (where x is Tin sulfide represented by positive real number), WS 2 and other formulas WS x (where x is a positive real number), tungsten sulfide represented by SbS x such as Sb 2 S 3 (where, x is antimony represented
- nitride examples include lithium-containing nitrides such as Li 3 N, Li 3-x A x N (where A is Ni and / or Co, and 0 ⁇ x ⁇ 3). Can be mentioned. These carbon materials, oxides, sulfides, and nitrides may be used in combination of two or more. These may be either crystalline or amorphous. Further, these carbon materials, oxides, sulfides, and nitrides are mainly carried on the negative electrode current collector and used as electrodes.
- the metal include lithium metal, silicon metal, and tin metal.
- the alloy include lithium alloys such as Li—Al, Li—Ni, and Li—Si, silicon alloys such as Si—Zn, Sn—Mn, Sn—Co, Sn—Ni, Sn—Cu, and Sn—La. And tin alloys such as Cu 2 Sb and La 3 Ni 2 Sn 7 . These metals and alloys are mainly used alone as electrodes (for example, used in a foil shape).
- carbon materials mainly composed of graphite such as natural graphite and artificial graphite are preferable.
- the shape of the carbon material may be any of a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder.
- the negative electrode mixture may contain a binder as necessary.
- the binder include thermoplastic resins, and specific examples include polyvinylidene fluoride, thermoplastic polyimide, carboxymethyl cellulose (hereinafter also referred to as CMC), polyethylene, and polypropylene.
- Examples of the negative electrode current collector include Cu, Ni, and stainless steel, and Cu may be used because it is difficult to form an alloy with lithium and it can be easily processed into a thin film.
- the method for supporting the negative electrode mixture on the negative electrode current collector is the same as in the case of the positive electrode, and is formed into a paste using a method by pressure molding or a solvent, and the obtained paste is applied onto the negative electrode current collector. For example, a method for obtaining a coated current collector and removing the solvent by drying, followed by pressing and pressure bonding may be mentioned.
- the separator for example, a member made of a material such as a polyolefin resin such as polyethylene or polypropylene, a fluororesin, or a nitrogen-containing aromatic polymer and having a form such as a porous film, a nonwoven fabric, or a woven fabric can be used.
- the separator may be made of two or more kinds of the materials, and the members may be laminated. Examples of the separator include separators described in JP-A No. 2000-30686 and JP-A No. 10-324758.
- the thickness of the separator is preferably as thin as possible as long as the mechanical strength is maintained, and is usually about 5 to 200 ⁇ m, preferably about 5 to 40 ⁇ m. .
- the separator preferably has a porous film containing a thermoplastic resin.
- the separator is disposed between the positive electrode and the negative electrode.
- the separator preferably has a function of blocking (shutdown) an excessive current from flowing when an abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode.
- the shutdown is performed by closing the micropores of the porous film in the separator when the normal use temperature is exceeded.
- a separator examples include a laminated film in which a heat resistant porous layer and a porous film are laminated.
- the heat resistance of the secondary battery can be further increased.
- the heat-resistant porous layer may be laminated on both surfaces of the porous film.
- the heat resistant porous layer is a layer having higher heat resistance than the porous film, and the heat resistant porous layer may be formed of an inorganic powder or may contain a heat resistant resin.
- the heat resistant porous layer contains a heat resistant resin, the heat resistant porous layer can be formed by an easy technique such as coating.
- the heat resistant resin include polyamide, polyimide, polyamideimide, polycarbonate, polyacetal, polysulfone, polyphenylene sulfide, polyetherketone, aromatic polyester, polyethersulfone, and polyetherimide, from the viewpoint of further improving heat resistance.
- polyamide, polyimide, polyamideimide, polyethersulfone, and polyetherimide are preferable, and polyamide, polyimide, and polyamideimide are more preferable.
- nitrogen-containing aromatic polymers such as aromatic polyamides (para-oriented aromatic polyamides, meta-oriented aromatic polyamides), aromatic polyimides, aromatic polyamideimides, and particularly preferred are aromatic polyamides and production surfaces.
- para-oriented aromatic polyamide hereinafter sometimes referred to as “para-aramid”.
- examples of the heat resistant resin include poly-4-methylpentene-1 and cyclic olefin polymers.
- the heat resistance of the laminated film that is, the thermal film breaking temperature of the laminated film can be further increased.
- the compatibility with the electrolytic solution may be good depending on the polarity in the molecule. In this case, the electrolytic solution is retained in the heat-resistant porous layer. Improves. Thereby, in manufacture of a nonaqueous electrolyte secondary battery, the injection
- the thermal film breaking temperature of the laminated film depends on the type of heat-resistant resin, and is selected and used according to the usage scene and purpose of use. More specifically, as the heat-resistant resin, the cyclic olefin polymer is used at about 400 ° C. when the nitrogen-containing aromatic polymer is used, and at about 250 ° C. when poly-4-methylpentene-1 is used. When using, the thermal film breaking temperature can be controlled to about 300 ° C., respectively. When the heat-resistant porous layer is made of an inorganic powder, the thermal film breaking temperature can be controlled to 500 ° C. or higher, for example.
- the para-aramid is obtained by condensation polymerization of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4′-biphenylene, 1 , 5-naphthalene, 2,6-naphthalene and the like, which are substantially composed of repeating units bonded in the opposite direction (orientation positions extending coaxially or in parallel).
- para-aramid having a structure according to the type.
- the aromatic polyimide is preferably a wholly aromatic polyimide produced by condensation polymerization of an aromatic dianhydride and a diamine.
- the dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic Examples include acid dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like.
- diamine examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, 1,5 -Naphthalenediamine and the like.
- a polyimide soluble in a solvent can be preferably used. Examples of such a polyimide include a polycondensate polyimide of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine.
- aromatic polyamideimide examples include those obtained by condensation polymerization of aromatic dicarboxylic acid and aromatic diisocyanate, and those obtained by condensation polymerization of aromatic dianhydride and aromatic diisocyanate.
- aromatic dicarboxylic acid examples include isophthalic acid and terephthalic acid.
- aromatic dianhydride examples include trimellitic anhydride.
- aromatic diisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylane diisocyanate, m-xylene diisocyanate, and the like.
- the heat-resistant porous layer is preferably thin, and specifically, preferably 1 ⁇ m to 10 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m, and particularly preferably 1 ⁇ m to 4 ⁇ m. .
- the heat-resistant porous layer has fine pores, and the size (diameter) of the pores is usually 3 ⁇ m or less, preferably 1 ⁇ m or less.
- the heat resistant porous layer may further contain a filler described later.
- the porous film preferably has fine pores and has a shutdown function.
- the porous film contains a thermoplastic resin.
- the size of the micropores in the porous film is usually 3 ⁇ m or less, preferably 1 ⁇ m or less.
- the porosity of the porous film is usually 30 to 80% by volume, preferably 40 to 70% by volume.
- the porous film containing the thermoplastic resin can close the micropores by softening the thermoplastic resin constituting the porous film.
- the thermoplastic resin that does not dissolve in the electrolyte in the nonaqueous electrolyte secondary battery may be selected.
- Specific examples include polyolefin resins such as polyethylene and polypropylene, and thermoplastic polyurethane resins, and a mixture of two or more of these may be used.
- the porous film preferably contains polyethylene.
- Specific examples of polyethylene include low density polyethylene, high density polyethylene, linear polyethylene, and the like, and ultrahigh molecular weight polyethylene having a molecular weight of 1,000,000 or more can also be exemplified.
- the thermoplastic resin constituting the film preferably contains ultra high molecular weight polyethylene.
- the thermoplastic resin may preferably contain a wax made of polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
- the thickness of the porous film in the laminated film is usually 3 to 30 ⁇ m, preferably 3 to 25 ⁇ m, more preferably 3 to 19 ⁇ m.
- the thickness of the laminated film is usually 5 ⁇ m to 40 ⁇ m, preferably 5 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m.
- the value of A / B is preferably 0.1 or more and 1 or less.
- the heat resistant porous layer may contain one or more fillers.
- the filler may be one or more selected from organic powder, inorganic powder, or a mixture thereof.
- the particles constituting the filler preferably have an average particle size of 0.01 ⁇ m or more and 1 ⁇ m or less.
- Examples of the organic powder include styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, and methyl acrylate, or a copolymer of two or more types; polytetrafluoroethylene, 4 fluorine, and the like.
- Fluorine resins such as fluorinated ethylene-6fluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, and polyvinylidene fluoride; melamine resin; urea resin; polyolefin; polymethacrylate; It is done.
- An organic powder may be used independently and can also be used in mixture of 2 or more types. Among these organic powders, polytetrafluoroethylene powder is preferable from the viewpoint of chemical stability.
- the inorganic powder examples include powders made of inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates, sulfates, etc. Among these, they are made of inorganic substances having low conductivity. Powder is preferably used. Specific examples include powders made of alumina, silica, titanium dioxide, calcium carbonate, or the like. The inorganic powder may be used alone or in combination of two or more. Among these inorganic powders, alumina powder is preferable from the viewpoint of chemical stability. More preferably, all of the particles constituting the filler are alumina particles.
- the particles constituting the filler are alumina particles, and part or all of them are substantially spherical alumina particles.
- the heat resistant porous layer is formed from an inorganic powder, the inorganic powder exemplified above may be used, and may be used by mixing with a binder as necessary.
- the filler content when the heat-resistant porous layer contains a heat-resistant resin depends on the specific gravity of the filler material.
- the weight of the filler is usually 5 or more and 95 or less, preferably 20 or more and 95 or less, more preferably 30 or more and 90 or less. These ranges can be appropriately set depending on the specific gravity of the filler material.
- Examples of the shape of the filler include a substantially spherical shape, a plate shape, a columnar shape, a needle shape, a whisker shape, and a fibrous shape, and any particle can be used. It is preferable that Examples of the substantially spherical particles include particles having a particle aspect ratio (particle major axis / particle minor axis) of 1 or more and 1.5 or less. The aspect ratio of the particles can be determined by an electron micrograph.
- the air permeability of the Gurley separator is preferably 50 to 300 seconds / 100 cc, more preferably 50 to 200 seconds / 100 cc.
- the separator has a porosity of usually 30 to 80% by volume, preferably 40 to 70% by volume.
- the separator may be a laminate of separators having different porosity.
- the electrolytic solution is usually composed of an organic solvent containing an electrolyte.
- the electrolyte include LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LIBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (COCF 3 ), Li (C 4 F 9 SO 3 ), LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , LiBOB (where BOB is bis (oxalato) borate) And lithium salts such as lower aliphatic carboxylic acid lithium salt and LiAlCl 4, and a mixture of two or more of these may be used.
- At least one fluorine selected from the group consisting of LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 and LiC (SO 2 CF 3 ) 3.
- LiPF 6 LiAsF 6
- LiSbF 6 LiBF 4
- LiCF 3 SO 3 LiN (SO 2 CF 3 ) 2
- LiC LiC
- examples of the organic solvent include propylene carbonate, ethylene carbonate (hereinafter sometimes referred to as EC), dimethyl carbonate (hereinafter sometimes referred to as DMC), diethyl carbonate, and ethyl methyl carbonate (hereinafter referred to as EMC).
- Carbonates such as 4-trifluoromethyl-1,3-dioxolan-2-one, 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3- Ethers such as dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; Nitriles such as tonitrile and butyronitrile; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; carbamates such as 3-methyl-2-oxazolidone; sulfolane, dimethyl sulfoxide and 1,3-propane sultone Or a sulfur-containing compound such as those obtained by further introducing a fluorine substituent into the above
- a mixed solvent in which two or more of these organic solvents are mixed is used.
- a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate or cyclic carbonate and ether is more preferable.
- the mixed solvent of cyclic carbonate and non-cyclic carbonate has a wide operating temperature range, excellent load characteristics, and is hardly decomposable even when a graphite material such as natural graphite or artificial graphite is used as the negative electrode active material.
- a mixed solvent containing EC, DMC and EMC is preferable.
- an electrolytic solution containing a fluorine-containing lithium salt such as LiPF 6 and an organic solvent having a fluorine substituent because a particularly excellent safety improvement effect is obtained.
- a mixed solvent containing ethers having fluorine substituents such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether and DMC is excellent in high current discharge characteristics, and more preferable. .
- a solid electrolyte may be used instead of the above electrolytic solution.
- the solid electrolyte for example, an organic polymer electrolyte such as a polyethylene oxide polymer, a polymer containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used.
- a so-called gel type in which an electrolyte is held in a polymer can also be used.
- An inorganic solid electrolyte containing a sulfide such as —Li 2 SO 4 may be used. Using these solid electrolytes, safety may be further improved.
- the solid electrolyte when a solid electrolyte is used, the solid electrolyte may serve as a separator, and in that case, the separator may not be required.
- the particle size distribution measurement, the BET specific surface area measurement, and the powder X-ray diffraction measurement for each powder were performed by the following methods.
- Example 1 (Preparation of positive electrode) As the positive electrode active material powder, one having an average particle diameter of 0.2 ⁇ m and a tap density of 1.8 g / cm 3 was used.
- the positive electrode active material powder was composed of a lithium composite metal oxide represented by Li 1.3 (Ni 0.41 Mn 0.49 Fe 0.10 ) O 2 , and the lithium composite metal oxide had an ⁇ -NaFeO 2 type crystal structure.
- As the conductive agent a non-graphite carbon material (acetylene black, manufactured by Denki Kagaku Kogyo Co., Ltd., trade name Denka Black HS100) having an average particle size of 0.05 ⁇ m was used. The bulk density of this carbon material was 0.15 g / cm 3 . PVdF was used as a binder. NMP was used as the solvent.
- As a current collector positive electrode current collector
- an Al foil having a thickness of 20 ⁇ m was used.
- a disperse mat manufactured by VMA-GETZMANN GMBH, trade name: DISPERMAT CN10F2 was used.
- the viscosity of the premixed product was 28000 mPa ⁇ s.
- a thin-film swirl type high-speed stirrer 90 ml of the premixed product was mixed and kneaded to obtain a positive electrode mixture.
- T.I. K. A Fillmix type 56-50 was used.
- the rotation conditions of the rotating wheel were a peripheral speed of 35 m / s and 30 seconds.
- the viscosity of the obtained positive electrode mixture was 12000 mPa ⁇ s.
- This positive electrode mixture was applied to both sides of an aluminum foil having a thickness of 15 ⁇ m to obtain a coated current collector, and the solvent was removed by drying the coated current collector to produce a positive electrode.
- the coating amount of the positive electrode mixture component per one side of the aluminum foil after drying was 16.5 mg / cm 2 . After pressing this with a roll press machine, an aluminum lead was welded.
- Natural graphite and artificial graphite were used as the negative electrode active material.
- CMC was used as a binder. These were weighed so that the weight ratio of natural graphite: artificial graphite: binder was 58.8: 39.2: 2, mixed and kneaded in water as a solvent to obtain a negative electrode mixture paste. It was.
- a disper mat manufactured by VMA-GETZMANN GMBH, trade name: DISPERMAT CN10F2
- mixing and kneading an appropriate amount of water was added so that the viscosity of the paste was 1000 to 3000 mPa ⁇ s.
- This negative electrode mixture was applied to both surfaces of a 10 ⁇ m thick copper foil to obtain a coated current collector, and the coated current collector was dried to remove the solvent, thereby producing a negative electrode.
- the coating amount of the negative electrode mixture component per one side of the copper foil after drying was 7.5 mg / cm 2 . After pressing this with a roll press, a copper lead was welded.
- a polypropylene porous film was used as the separator.
- the positive electrode, the separator, the negative electrode, and the separator were laminated in this order and wound in a spiral shape to produce an electrode group.
- the battery size of the electrode group was 62 mm in length, 35 mm in width, and 3.6 mm in thickness.
- the electrode group was inserted into an aluminum laminate battery container.
- a non-aqueous electrolyte secondary battery having a design capacity of 600 mAh was manufactured by pouring a predetermined amount of electrolyte into the battery container into which the electrode group was inserted.
- the design capacity of 600 mAh means that the design is such that the discharge capacity is 600 mAh when discharged at a 0.2 C rate.
- Comparative Example 1 As the positive electrode active material powder, except that LiCoO 2 powder having a tap density of 2.0 g / cm 3 and an average particle diameter of 3.0 ⁇ m (manufactured by Nippon Chemical Industry Co., Ltd., trade name Cell Seed) was used, A positive electrode mixture was produced in the same manner as in Example 1. The viscosity of this positive electrode mixture was 2000 mPa ⁇ s.
- Example 1 Using this positive electrode mixture, a positive electrode was obtained in the same manner as in Example 1, and a nonaqueous electrolyte secondary battery having a design capacity of 600 mAh was manufactured in the same manner as in Example 1.
- Comparative Example 2 A nonaqueous electrolyte secondary battery having a design capacity of 600 mAh was manufactured in the same manner as in Example 1 except that the premixed product in Example 1 was used as it was as the positive electrode mixture.
- Example 2 Evaluation of non-aqueous electrolyte secondary battery
- the discharge rate test is a test for measuring the discharge capacity by changing the discharge current at the time of discharge, and the discharge capacity retention rate was calculated according to the following formula.
- Discharge capacity retention rate discharge capacity at each cycle (each discharge rate) / discharge capacity at the second cycle (0.2 C rate) ⁇ 100
- the nonaqueous electrolyte secondary battery of Example 1 of the present invention is higher in input / output characteristics at a higher current rate than the nonaqueous electrolyte secondary batteries of Comparative Examples 1 and 2. It is understood that is superior.
- Production Example 1 (Production of laminated film) (1) Production of coating solution After 272.7 g of calcium chloride was dissolved in 4200 g of NMP, 132.9 g of paraphenylenediamine was added thereto and completely dissolved. To the obtained solution, 243.3 g of terephthalic acid dichloride was gradually added and polymerized to obtain para-aramid, which was further diluted with NMP to obtain a para-aramid solution (A) having a concentration of 2.0% by weight.
- alumina powder (a) manufactured by Nippon Aerosil Co., Ltd., Alumina C, average particle size 0.02 ⁇ m
- alumina powder (b) Sumiko Random, AA03, average particles 4 g in total as a filler was added and mixed, treated three times with a nanomizer, filtered through a 1000 mesh wire net, and degassed under reduced pressure to produce a coating slurry (B).
- the weight of alumina powder (filler) with respect to the total weight of para-aramid and alumina powder is 67% by weight.
- a polyethylene porous film (film thickness 12 ⁇ m, air permeability 140 seconds / 100 cc, average pore diameter 0.1 ⁇ m, porosity 50%) was used.
- the polyethylene porous film was fixed on a PET film having a thickness of 100 ⁇ m, and the coating slurry (B) was applied onto the porous film with a bar coater manufactured by Tester Sangyo Co., Ltd.
- the PET film and the coated porous film are integrated and immersed in water to precipitate a para-aramid porous film (heat-resistant porous layer), and then the solvent is dried to form the heat-resistant porous layer and the porous film.
- a laminated film 1 was obtained.
- the thickness of the laminated film 1 was 16 ⁇ m, and the thickness of the para-aramid porous film (heat resistant porous layer) was 4 ⁇ m.
- the air permeability of the laminated film 1 was 180 seconds / 100 cc, and the porosity was 50%.
- SEM scanning electron microscope
- a non-aqueous electrolyte secondary battery capable of further increasing the thermal film breaking temperature can be obtained using the laminated film obtained in Production Example 1 as a separator.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
<1> 正極活物質粉末、導電剤、バインダーおよび溶剤を含む正極合剤であって、
正極活物質粉末が、平均粒径が0.05μm以上1μm以下の粒子から構成され、
正極活物質粉末が、0.8~3.0g/cm3のタップ密度を有し、
正極活物質粉末100重量部に対する導電剤の量が、0.5~20重量部であり、
正極活物質粉末100重量部に対するバインダーの量が、0.5~10重量部であり、
正極活物質粉末100重量部に対する溶剤の量が、10~120重量部であり、かつ、
粘度が、1000~25000mPa・sである、
正極合剤。
<2> 正極活物質粉末、導電剤およびバインダーの合計重量に対する正極活物質粉末の重量割合が、77~99重量%である<1>の正極合剤。
<3> 正極活物質粉末が、2~30m2/gのBET比表面積を有する<1>または<2>の正極合剤。
<4> 正極活物質粉末が、NiおよびMnを含有するリチウム複合金属酸化物で構成される<1>~<3>のいずれかの正極合剤。
<5> リチウム複合金属酸化物が、以下の式(A)で表される<4>の正極合剤。
Liα(Ni1-(x+y+z)MnxFeyCoz)O2 (A)
(ここで、0<x<1、0≦y<1、0≦z<1、0<x+y+z<1、0.5≦α≦1.5である。)
<6> yが、0を超え0.2以下の範囲内である<5>の正極合剤。
<7> 導電剤が、炭素材料である<1>~<6>のいずれかの正極合剤。
<8> 導電材が0.01~1.3g/cm3のかさ密度を有する<1>~<7>のいずれかの正極合剤。
<9> バインダーが、-30℃~-40℃のガラス転移温度を有する<1>~<8>のいずれかの正極合剤。
<10> バインダーが、ポリフッ化ビニリデンで構成される<1>~<9>のいずれかの正極合剤。
<11> バインダーおよび溶剤の合計重量に対するバインダーの重量割合が、1~20重量%である<1>~<10>のいずれかの正極合剤。
<12> 溶剤が、0.935~1.200g/cm3の密度を有する<1>~<11>のいずれかの正極合剤。
<13> <1>~<12>のいずれかの正極合剤を集電体に塗工して塗工集電体を得て、該塗工集電体から溶剤を除去して製造された正極。
<14> <13>の正極を有する非水電解質二次電池。
本発明の正極合剤は、正極活物質粉末、導電剤、バインダーおよび溶剤を含む。該正極活物質粉末は、平均粒径が0.05μm以上1μm以下の粒子から構成される。該正極活物質粉末は、0.8~3.0g/cm3のタップ密度を有する。正極活物質粉末100重量部に対する導電剤の量は、0.5~20重量部である。正極活物質粉末100重量部に対するバインダーの量は、0.5~10重量部である。正極活物質粉末100重量部に対する溶剤の量は、10~120重量部である。正極合剤の粘度は、1000~25000mPa・sである。本発明の正極合剤は、非水電解質二次電池に好適に使用される。
正極活物質粉末は、通常、一次粒子および一次粒子の凝集粒子から構成される。正極活物質粉末を構成する粒子の平均粒径は、0.05μm以上、又は0.10μm以上であって、1μm以下、0.7μm以下、0.5μm以下である。平均粒径は、レーザー回折粒度分布測定により決定されたD50の値である。レーザー回折粒度分布測定の装置としては、マルバーン社製のレーザー回折式粒度分布測定装置(型式:マスターサイザー2000)が挙げられる。正極活物質粉末を構成する粒子の平均粒径が小さすぎると、電解液との反応性の観点で問題が生じる場合がある。また、この平均粒径が、大きすぎると高出力の電池を得難くなる傾向にある。
正極活物質粉末のタップ密度は0.8g/cm3以上、1.0g/cm3以上、又は1.5g/cm3以上であって、3.0g/cm3以下である。タップ密度は、メスシリンダーに定めた重量の正極活物質粉末を投入して、これらを200回タップしたときの粒子および粒子間空隙の合計体積を読み取り、前記正極活物質重量を前記合計体積で除して決定される。株式会社セイシン企業のタップデンサーKYT4000を用いてタップ密度を決定することもできる。正極活物質粉末のタップ密度が小さすぎると、得られる正極の体積あたりの正極活物質量が少なくなり、正極のエネルギー密度が低下する傾向にある。タップ密度の上限は、3.0g/cm3である。
本発明の正極合剤は、上記正極活物質粉末、導電剤、バインダーおよび溶剤を特定量比で含み、1000Pa・s以上、3000mPa・s以上、5000mPa・s以上、又は8000mPa・s以上であって、25000mPa・s以下、又は20000mPa・s以下の粘度を有する。本発明の正極合剤を用いて得られる正極を非水電解質二次電池に用いれば、高い電流レートでより高出力を示す非水電解質二次電池、すなわち、出力特性により優れる電池を得ることができる。
正極活物質粉末100重量部に対する導電剤の量は、0.5重量部以上、1重量部以上、又は3重量部以上であって、20重量部以下、15重量部以下、又は20重量部以下である。導電剤の量が少なすぎると、得られる正極の導電性が低下する傾向にある。また、導電剤の量が多すぎると、正極の重量あたりの正極活物質量が少なくなり、正極のエネルギー密度が低下する傾向にある。
正極活物質粉末100重量部に対するバインダーの量は、0.5重量部以上、重量部以上、1重量部以上、又は3重量部以上であって、10重量部以下である。バインダーの量が少なすぎると、正極合剤の集電体への接着力の点で好ましくない。また、バインダーの量が多すぎると、正極の重量あたりの正極活物質量が少なくなり、正極のエネルギー密度が低下する傾向にある。
正極活物質粉末100重量部に対する溶剤の量は、10重量部以上、又は20重量部以上であって、120重量部、又は100重量部以下である。溶剤の量が少なすぎると、集電体への塗工が困難となる傾向にある。また、溶剤の量が多すぎると、塗工した後の乾燥が困難となる傾向にある。
正極活物質粉末重量、導電剤重量およびバインダー重量の合計重量に対する正極活物質粉末の重量割合が、77重量%、80重量%、又は90重量%であって、99重量%以下、又は95重量%以下であることが好ましい。正極活物質粉末の重量割合が前記範囲であることで、得られる電池の放電容量および出力特性をより高めることができる。
正極活物質粉末は、2~30m2/gのBET比表面積を有することが好ましい。正極活物質粉末のBET比表面積が前記範囲であることで、得られる電池の出力特性がより高まり、後述の電解液との反応性がより抑制されることができる。
本発明における正極活物質粉末についてより具体的に説明する。資源面で環境にやさしく、かつ、容量の高い非水電解質二次電池を得る観点で、正極活物質粉末は、NiおよびMnを含有するリチウム複合金属酸化物で構成されることが好ましい。
Liα(Ni1-(x+y+z)MnxFeyCoz)O2 (A)
(ここで、0<x<1、0≦y<1、0≦z<1、0<x+y+z<1、0.5≦α≦1.5である。)
Liα(Ni1-(x+y)MnxFey)O2 (B)
(ここで、0<x<1、0≦y<1、0<x+y<1、0.5≦α≦1.5である。)
次に本発明における正極活物質粉末を製造する方法を具体的に説明する。NiおよびMnを含有するリチウム複合金属酸化物の粉末を製造する方法の例を説明する。
NiおよびMnを含有するリチウム複合金属酸化物の粉末は、共沈物およびリチウム化合物の混合物を900℃以下の温度で保持して焼成することにより製造することができる。その共沈物は、Ni、MnおよびCl、必要に応じてFe、Coを含有する水溶液(以下、「第1水溶液」ともいう。)とアルカリとを接触させることにより得られる。共沈物は、前記接触時に、共沈物の粉体として得られてもよいが、共沈物スラリーとして得られることが好ましい。得られる共沈物の形状は、第1水溶液におけるNi、Mn、Fe、Coの濃度、第1水溶液と接触させるアルカリの形態(水溶液状または固体)に依存する。なお、第1水溶液、アルカリ、第1水溶液と該アルカリとの接触方法、リチウム化合物と共沈物との混合方法、混合物の焼成方法などについては、後述のもの、あるいは方法を用いることができる。
共沈の代わりに、混合を行ってもよい。この場合、正極活物質粉末は、金属化合物混合物を焼成することにより製造することができる。まず、対応する金属元素を含有する化合物を、所定の組成となるように秤量し、混合して、金属化合物混合物を得る。次に、金属化合物混合物を焼成することにより、正極活物質粉末を製造することができる。本発明に使用する正極活物質粉末としてのリチウム複合金属酸化物の粉末の製造方法としては、前記の共沈物を得る工程を有する方法が、目的の粉末特性を得られやすく、より好ましい。
(1)第1水溶液とアルカリとを接触させて共沈物スラリーを得る工程。
(2)該共沈物スラリーから、共沈物を得る工程。
(3)該共沈物とリチウム化合物とを混合して得られる混合物を900℃以下の温度で保持して焼成してリチウム複合金属酸化物を得る工程。
(2´)該共沈物スラリーを固液分離後、得られる固形分を洗浄、乾燥して、共沈物を得る工程。
本発明の正極合剤における導電剤は、好ましくは炭素材料である。炭素材料の例としては、黒鉛あるいは非黒鉛炭素材料などを挙げることができ、炭素材料は、単一成分または混合成分からなっていてもよい。導電剤のかさ密度は好ましくは0.01~1.3g/cm3である。かさ密度は、メスシリンダーに定めた重量の導電剤を投入して、これらをタップすることなく、粒子および粒子間空隙の合計体積を読み取り、前記導電剤重量を前記合計体積で除して決定される。株式会社セイシン企業製のマルチテスターMT-1001を用いてかさ密度を決定することもできる。導電剤のかさ密度が前記の範囲であることで、得られる二次電池の放電容量を、容易に、より高めることが可能である。
黒鉛の例として、具体的には、天然黒鉛、人造黒鉛等の黒鉛が挙げられる。
非黒鉛炭素材料の例としては、カーボンブラック、アセチレンブラックなどが挙げられる。繊維状炭素材料を用いてもよい。繊維状炭素材料の例として、具体的には、黒鉛化炭素繊維、カーボンナノチューブが挙げられる。カーボンナノチュ-ブは、シングルウォール、マルチウォールのいずれでもよい。繊維状炭素材料は、市販されているものを、適宜、粉砕して用いてもよい。粉砕は、乾式、湿式のいずれによってもよい。乾式粉砕としては、ボールミル、ロッキングミル、遊星ボールミルによる粉砕が挙げられ、湿式粉砕としては、ボールミル、デイスパ-マットによる粉砕が挙げられる。
本発明の正極合剤におけるバインダーとしては、熱可塑性樹脂が挙げられる。熱可塑性樹脂の例として、具体的には、ポリフッ化ビニリデン(以下、PVdFともいう。)、ポリテトラフルオロエチレン(以下、PTFEともいう)、四フッ化エチレン・六フッ化プロピレン・フッ化ビニリデン系共重合体、六フッ化プロピレン・フッ化ビニリデン系共重合体、四フッ化エチレン・パーフルオロビニルエーテル系共重合体などのフッ素樹脂、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂等が挙げられる。バインダーは、好ましくはポリフッ化ビニリデンである。二種以上のバインダーを混合してもよい。バインダーはフッ素樹脂およびポリオレフィン樹脂であることが好ましく、これにより集電体との結着性により優れた正極合剤を得ることができる。バインダーは、後述の溶剤に溶解または分散させて用いることができる。
本発明の正極合剤における溶剤の例としては、N,N―ジメチルアミノプロピルアミン、ジエチレントリアミン、N,N―ジメチルホルムアミド(以下、DMFともいう)等のアミン系溶剤、テトラヒドロフラン)等のエーテル系溶剤、メチルエチルケトン等のケトン系溶剤、酢酸メチル等のエステル系溶剤、ジメチルアセトアミド、1-メチル-2-ピロリドン(以下、NMPともいう)等のアミド系溶剤、ジメチルスルホキシド(以下、DMSO)等が挙げられる。
次に、本発明の正極合剤を製造する方法を説明する。本発明の電極合剤は、次の正極活物質粉末、導電剤、バインダーおよび溶剤を、後述の手法により混合・混練することにより製造できる:
正極活物質粉末は、平均粒径が0.05μm以上1μm以下の粒子から構成され、かつ0.8~3.0g/cm3のタップ密度を有し、
正極活物質粉末100重量部に対する導電剤の量が0.5~20重量部であり、
正極活物質粉末100重量部に対するバインダーの量が0.5~10重量部であり、
正極活物質粉末100重量部に対する溶剤の量が10~120重量部である。
上記の正極合剤を集電体に塗工して塗工集電体を得て、該塗工集電体から溶剤を除去して、正極を製造することができる。溶剤の除去は、乾燥により行われてもよい。集電体(以下、正極集電体ともいう。)の例としては、Al、Ni、ステンレスなどが挙げられる。薄膜に加工しやすく、安価であるという点でAlが好ましい。溶剤を除去した後、正極をプレスしてもよい。正極合剤を集電体に塗工する方法としては、例えば、ダイ塗工法、スクリーン塗工法、カーテン塗工法、ナイフ塗工法、グラビア塗工法、静電スプレー法等が挙げられる。
次に、上記正極を有する非水電解質二次電池について、説明する。非水電解質二次電池は、正極と、負極と、電解質を有し、さらに必要に応じてセパレータを有する。該電池の例としてリチウム二次電池が挙げられる。
リチウム二次電池は、セパレータ、上述の正極、セパレータ、および負極を、積層または積層かつ巻回することにより得られる電極群を、電池缶などの電池ケース内に収納した後、該ケース内に電解質を含有する有機溶媒からなる電解液を注入することにより製造することができる。
前記負極は、正極よりも低い電位でリチウムイオンのドープかつ脱ドープが可能であればよく、負極材料を含む負極合剤が負極集電体に担持された電極、または負極材料単独からなる電極を挙げることができる。負極材料としては、炭素材料、カルコゲン化合物(酸化物、硫化物など)、窒化物、金属または合金であって、正極よりも低い電位でリチウムイオンのドープかつ脱ドープが可能な材料が挙げられる。また、2種以上の負極材料を混合して用いてもよい。
前記セパレータとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂、フッ素樹脂、含窒素芳香族重合体などの材料からなる、多孔質膜、不織布、織布などの形態を有する部材を用いることができる。セパレータは、2種以上の前記材料からなっていてもよいし、前記部材が積層されていてもよい。セパレータとしては、例えば特開2000-30686号公報、特開平10-324758号公報等に記載のセパレータを挙げることもできる。セパレータの厚みは、電池の体積エネルギー密度が上がりかつ内部抵抗が小さくなるという観点で、機械的強度が保たれる限り薄くした方がよく、通常5~200μm程度、好ましくは5~40μm程度である。
セパレータは、好ましくは、熱可塑性樹脂を含有する多孔質フィルムを有する。非水電解質二次電池において、セパレータは、正極と負極の間に配置される。セパレータは、正極-負極間の短絡等が原因で電池内に異常電流が流れた際に、電流を遮断して、過大電流が流れることを阻止(シャットダウン)する機能を有することが好ましい。ここで、シャットダウンは、通常の使用温度を越えた場合に、セパレータにおける多孔質フィルムの微細孔を閉塞することによりなされる。そしてシャットダウンした後、ある程度の高温まで電池内の温度が上昇しても、その温度により破膜することなく、シャットダウンした状態を維持することが好ましい。かかるセパレータとしては、耐熱多孔層と多孔質フィルムとが積層された積層フィルムが挙げられる。該フィルムをセパレータとして用いることにより、二次電池の耐熱性をより高めることが可能でなる。ここで、耐熱多孔層は、多孔質フィルムの両面に積層されていてもよい。
二次電池において、電解液は、通常、電解質を含有する有機溶媒からなる。電解質の例としては、LiClO4、LiPF6、LiAsF6、LiSbF6、LIBF4、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2CF3)(COCF3)、Li(C4F9SO3)、LiC(SO2CF3)3、Li2B10Cl10、LiBOB(ここで、BOBは、bis(oxalato)borateのことである。)、低級脂肪族カルボン酸リチウム塩、LiAlCl4などのリチウム塩が挙げられ、これらの2種以上の混合物を使用してもよい。通常、これらの中でもLiPF6、LiAsF6、LiSbF6、LiBF4、LiCF3SO3、LiN(SO2CF3)2およびLiC(SO2CF3)3からなる群から選ばれる1種以上のフッ素含有リチウム塩を用いる。
上記の電解液の代わりに固体電解質を用いてもよい。固体電解質としては、例えばポリエチレンオキサイド系の高分子、ポリオルガノシロキサン鎖もしくはポリオキシアルキレン鎖の少なくとも一種以上を含む高分子などの有機系高分子電解質を用いることができる。高分子に電解液を保持させた、いわゆるゲルタイプのものを用いることもできる。Li2S-SiS2、Li2S-GeS2、Li2S-P2S5、Li2S-B2S3、Li2S-SiS2-Li3PO4、Li2S-SiS2-Li2SO4などの硫化物を含む無機系固体電解質を用いてもよい。これら固体電解質を用いて、安全性をより高めることができることがある。本発明の非水電解質二次電池において、固体電解質を用いる場合には、固体電解質がセパレータの役割を果たす場合もあり、その場合には、セパレータを必要としないこともある。
レーザー回折式粒度分布測定装置(型式:マスターサイザー2000、マルバーン社製)を用いて、正極活物質粉末のD50(μm)を測定し、この値を平均粒径とした。
(2)黒鉛粉末の平均粒径測定
レーザー回折式粒度分布測定装置(型式:マスターサイザー2000、マルバーン社製)を用いて、黒鉛粉末のD50(μm)を測定し、この値を平均粒径とした。
粉末1gを窒素気流中150℃、15分間乾燥した後、マイクロメリティクス製フローソーブII2300を用いて、粉末のBET比表面積を測定した。
正極活物質粉末の粉末X線回折測定は、粉末X線回折測定装置(株式会社リガク製RINT2500TTR型)を用いて行った。粉末を専用の基板に充填し、CuKα線源を用いて、回折角2θ=10°~90°の範囲で測定を行い、粉末X線回折図形を得た。粉末X線回折図形により、正極活物質粉末の結晶構造を同定した。
(正極の作製)
正極活物質粉末として、平均粒径が0.2μmで、タップ密度1.8g/cm3のものを用いた。正極活物質粉末は、Li1.3(Ni0.41Mn0.49Fe0.10)O2で表されるリチウム複合金属酸化物で構成され、該リチウム複合金属酸化物は、α-NaFeO2型結晶構造を有した。
導電剤として、平均粒径が0.05μmの非黒鉛炭素材料(アセチレンブラック、電気化学工業株式会社製、商品名デンカブラックHS100)を用いた。この炭素材料のかさ密度は0.15g/cm3であった。
バインダーとして、PVdFを用いた。
溶剤として、NMPを用いた。
集電体(正極集電体)として、厚さ20μmのAl箔を用いた。
負極活物質として、天然黒鉛および人造黒鉛を用いた。バインダーとしてCMCを用いた。これらを、天然黒鉛:人造黒鉛:バインダーの重量比が、58.8:39.2:2の割合になるように秤量し、溶媒である水中で混合・混練して、負極合剤ペーストを得た。混合・混練には、ディスパーマット(VMA-GETZMANN GMBH製、商品名DISPERMAT CN10F2)を用いた。混合・混練の際には、ペーストの粘度が1000~3000mPa・sになるように水を適量添加した。
セパレータとして、ポリプロピレン製多孔質フィルムを用いた。上記の正極、セパレータ、負極、セパレータをこの順に積層し、渦巻状に巻回し、電極群を作製した。電極群の電池サイズは、長さ62mm、幅35mm、厚さ3.6mmであった。電極群をアルミラミネートの電池容器に挿入した。電極群を挿入した電池容器に、電解液を所定量注液して、設計容量600mAhの非水電解質二次電池を製造した。設計容量600mAhとは、0.2Cレートで放電したときの放電容量が600mAhとなるように設計したことを意味する。
正極活物質粉末として、タップ密度が2.0g/cm3であり、かつ平均粒径が3.0μmであるLiCoO2粉末(日本化学工業(株)製、商品名セルシード)を用いた以外は、実施例1と同様にして正極合剤を作製した。この正極合剤の粘度は、2000mPa・sであった。
実施例1における予備混合品を、そのまま正極合剤として用いた以外は、実施例1と同様にして、設計容量600mAhの非水電解質二次電池を製造した。
上記実施例1、比較例1および比較例2により得られたそれぞれの非水電解質二次電池を用いて、以下に示す条件で放電レート試験を実施した。放電レート試験は、放電時の放電電流を変えて放電容量を測定する試験であり、以下の式に従い、放電容量維持率を計算した。
<放電レート試験>
試験温度:25℃
充電:充電最大電圧4.2V、充電時間4時間(1C)
放電:放電最小電圧を2.5Vで一定とし、各サイクルにおける放電電流を下記のように変えた。5C、10Cにおける放電(高い電流レート)による放電容量が高ければ高いほど、高い電流レートで高出力が示されたことを意味する。
1、2サイクル目の放電:0.2C
3サイクル目の放電:1C
4サイクル目の放電:5C
5サイクル目の放電:10C
<放電容量維持率>
放電容量維持率(%)=各サイクル(各放電レート)における放電容量/2サイクル目(0.2Cレート)の放電容量×100
実施例1の非水電解質二次電池を用いて、上記評価により、放電容量維持率を計算した結果、1Cの放電容量維持率は95%、5Cの放電容量維持率は90%、10Cの放電容量維持率は88%であった。
比較例1の非水電解質二次電池を用いて、上記評価により、放電容量維持率を計算した結果、1Cの放電容量維持率は95%、5Cの放電容量維持率は50%、10Cの放電容量維持率は1%であった。
比較例2の非水電解質二次電池を用いて、上記評価により、放電容量維持率を計算した結果、1Cの放電容量維持率は90%、5Cの放電容量維持率は60%、10Cの放電容量維持率は30%であった。
(1)塗工液の製造
NMP4200gに塩化カルシウム272.7gを溶解した後、これにパラフェニレンジアミン132.9gを添加して完全に溶解させた。得られた溶液に、テレフタル酸ジクロライド243.3gを徐々に添加して重合し、パラアラミドを得て、さらにNMPで希釈して、濃度2.0重量%のパラアラミド溶液(A)を得た。得られたパラアラミド溶液100gに、アルミナ粉末(a)2g(日本アエロジル社製、アルミナC、平均粒子径0.02μm)とアルミナ粉末(b)2g(住友化学株式会社製スミコランダム、AA03、平均粒子径0.3μm)とをフィラーとして計4g添加して混合し、ナノマイザーで3回処理し、さらに1000メッシュの金網で濾過、減圧下で脱泡して、塗工スラリー(B)を製造した。パラアラミドおよびアルミナ粉末の合計重量に対するアルミナ粉末(フィラー)の重量は、67重量%となる。
多孔質フィルムとしては、ポリエチレン製多孔質フィルム(膜厚12μm、透気度140秒/100cc、平均孔径0.1μm、空孔率50%)を用いた。厚み100μmのPETフィルムの上に上記ポリエチレン製多孔質フィルムを固定し、テスター産業株式会社製バーコーターにより、該多孔質フィルムの上に塗工スラリー(B)を塗工した。PETフィルムと塗工された該多孔質フィルムを一体にしたまま、水中に浸漬させ、パラアラミド多孔質膜(耐熱多孔層)を析出させた後、溶媒を乾燥させて、耐熱多孔層と多孔質フィルムとが積層された積層フィルム1を得た。積層フィルム1の厚みは16μmであり、パラアラミド多孔質膜(耐熱多孔層)の厚みは4μmであった。積層フィルム1の透気度は180秒/100cc、空孔率は50%であった。積層フィルム1における耐熱多孔層の断面を走査型電子顕微鏡(SEM)により観察をしたところ、0.03μm~0.06μm程度の比較的小さな微細孔と0.1μm~1μm程度の比較的大きな微細孔とを有することがわかった。尚、積層フィルムの評価は以下の方法で行った。
(A)厚み測定
積層フィルムの厚み、多孔質フィルムの厚みは、JIS規格(K7130-1992)に従い、測定した。また、耐熱多孔層の厚みとしては、積層フィルムの厚みから多孔質フィルムの厚みを差し引いた値を用いた。
(B)ガーレー法による透気度の測定
積層フィルムの透気度は、JIS P8117に基づいて、株式会社安田精機製作所製のデジタルタイマー式ガーレー式デンソメータで測定した。
(C)空孔率
得られた積層フィルムのサンプルを一辺の長さ10cmの正方形に切り取り、重量W(g)と厚みD(cm)を測定した。サンプル中のそれぞれの層の重量(Wi(g))を求め、Wiとそれぞれの層の材質の真比重(真比重i(g/cm3))とから、それぞれの層の体積を求めて、次式より空孔率(体積%)を求めた。
空孔率(体積%)=100×{1-(W1/真比重1+W2/真比重2+・・+Wn/真比重n)/(10×10×D)}
Claims (14)
- 正極活物質粉末、導電剤、バインダーおよび溶剤を含む正極合剤であって、
正極活物質粉末が、平均粒径が0.05μm以上1μm以下の粒子から構成され、
正極活物質粉末が、0.8~3.0g/cm3のタップ密度を有し、
正極活物質粉末100重量部に対する導電剤の量が、0.5~20重量部であり、
正極活物質粉末100重量部に対するバインダーの量が、0.5~10重量部であり、
正極活物質粉末100重量部に対する溶剤の量が、10~120重量部であり、かつ
粘度が、1000~25000mPa・sである、
正極合剤。 - 正極活物質粉末、導電剤およびバインダーの合計重量に対する正極活物質粉末の重量割合が、77~99重量%である請求項1記載の正極合剤。
- 正極活物質粉末が、2~30m2/gのBET比表面積を有する請求項1または2記載の正極合剤。
- 正極活物質粉末が、NiおよびMnを含有するリチウム複合金属酸化物で構成される請求項1~3のいずれかに記載の正極合剤。
- リチウム複合金属酸化物が、以下の式(A)で表される請求項4記載の正極合剤。
Liα(Ni1-(x+y+z)MnxFeyCoz)O2 (A)
(ここで、0<x<1、0≦y<1、0≦z<1、0<x+y+z<1、0.5≦α≦1.5である。) - yが、0を超え0.2以下の範囲内である請求項5記載の正極合剤。
- 導電剤が、炭素材料である請求項1~6のいずれかに記載の正極合剤。
- 導電材が0.01~1.3g/cm3のかさ密度を有する請求項1~7のいずれかに記載の正極合剤。
- バインダーが、-30℃~-40℃のガラス転移温度を有する請求項1~8のいずれかに記載の正極合剤。
- バインダーが、ポリフッ化ビニリデンで構成される請求項1~9のいずれかに記載の正極合剤。
- バインダーおよび溶剤の合計重量に対するバインダーの重量割合が、1~20重量%である請求項1~10のいずれかに記載の正極合剤。
- 溶剤が、0.935~1.200g/cm3の密度を有する請求項1~11のいずれかに記載の正極合剤。
- 請求項1~12のいずれか記載の正極合剤を集電体に塗工して塗工集電体を得て、該塗工集電体から溶剤を除去して製造された正極。
- 請求項13記載の正極を有する非水電解質二次電池。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/498,274 US20120183850A1 (en) | 2009-09-28 | 2010-09-24 | Positive electrode mixture, positive electrode and nonaqueous electrolyte secondary battery |
CN2010800428122A CN102576862A (zh) | 2009-09-28 | 2010-09-24 | 正极合剂、正极及非水电解质二次电池 |
EP10818873.1A EP2485303A4 (en) | 2009-09-28 | 2010-09-24 | POSITIVE ELECTRODE MIXTURE, POSITIVE ELECTRODE AND SECONDARY BATTERY WITH A WATER-FREE ELECTROLYTE |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009222134A JP2011070994A (ja) | 2009-09-28 | 2009-09-28 | 正極合剤、正極および非水電解質二次電池 |
JP2009-222134 | 2009-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011037201A1 true WO2011037201A1 (ja) | 2011-03-31 |
Family
ID=43795945
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2010/066586 WO2011037201A1 (ja) | 2009-09-28 | 2010-09-24 | 正極合剤、正極および非水電解質二次電池 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20120183850A1 (ja) |
EP (1) | EP2485303A4 (ja) |
JP (1) | JP2011070994A (ja) |
KR (1) | KR20120081982A (ja) |
CN (1) | CN102576862A (ja) |
WO (1) | WO2011037201A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113546569A (zh) * | 2021-08-03 | 2021-10-26 | 广东特顺能源设备有限公司 | 一种电池生产专用设备搅拌机 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6090662B2 (ja) * | 2012-06-29 | 2017-03-08 | 株式会社Gsユアサ | リチウム二次電池用正極活物質、その製造方法、リチウム二次電池用電極、リチウム二次電池 |
US20150333325A1 (en) * | 2012-11-19 | 2015-11-19 | Iucf-Hyu(Industry-University Cooperation Foundation Hanyang University) | Manufacturing method of positive active material precursor for sodium rechargeable batteries, positive active material precursor for sodium rechargeable batteries made by the same, and manufacturing method of positive active material for sodium rechargeable batteries, positive active material for sodium rechargeable batteries made by the same |
JP2014165096A (ja) * | 2013-02-27 | 2014-09-08 | Nippon Zeon Co Ltd | リチウムイオン二次電池耐熱層用スラリーの製造方法及びリチウムイオン二次電池用電極の製造方法 |
JP2014220074A (ja) * | 2013-05-07 | 2014-11-20 | 凸版印刷株式会社 | 非水電解質二次電池用正極、非水電解質二次電池及び非水電解質二次電池用正極の製造方法 |
JP6070421B2 (ja) | 2013-05-31 | 2017-02-01 | ソニー株式会社 | 電池、電池パック、電子機器、電動車両、蓄電装置および電力システム |
US10886533B2 (en) | 2016-01-22 | 2021-01-05 | Asahi Kasei Kabushiki Kaisha | Nonaqueous lithium power storage element |
CN110391094B (zh) | 2016-01-22 | 2021-10-12 | 旭化成株式会社 | 非水系锂型蓄电元件 |
JP6262402B2 (ja) | 2016-01-22 | 2018-01-17 | 旭化成株式会社 | 非水系リチウム蓄電素子 |
TWI629819B (zh) | 2016-01-22 | 2018-07-11 | 旭化成股份有限公司 | Non-aqueous lithium storage element |
KR101903939B1 (ko) * | 2016-01-22 | 2018-10-02 | 아사히 가세이 가부시키가이샤 | 정극 전구체 |
WO2017126691A1 (ja) | 2016-01-22 | 2017-07-27 | 旭化成株式会社 | 非水系リチウム型蓄電素子 |
JP6264429B2 (ja) * | 2016-11-07 | 2018-01-24 | 株式会社村田製作所 | 電池、電池パック、電子機器、電動車両、蓄電装置および電力システム |
CN109863629B (zh) * | 2017-06-27 | 2022-02-08 | 株式会社Lg化学 | 用于制备锂二次电池用的正极浆料的方法和由此获得的用于锂二次电池的正极 |
US11967709B2 (en) | 2017-10-31 | 2024-04-23 | Sumitomo Metal Mining Co., Ltd. | Nonaqueous electrolyte secondary battery positive electrode active material and method for producing same, and nonaqueous electrolyte secondary battery which uses positive electrode active material |
US11784310B2 (en) | 2017-10-31 | 2023-10-10 | Sumitomo Metal Mining Co., Ltd. | Non-aqueous electrolyte secondary battery positive electrode active material, method for producing same, and non-aqueous electrolyte secondary battery which uses positive electrode active material |
JP7240614B2 (ja) | 2017-10-31 | 2023-03-16 | 住友金属鉱山株式会社 | 非水系電解質二次電池用正極活物質とその製造方法、及び正極活物質を用いた非水系電解質二次電池 |
CN111316477B (zh) * | 2017-12-08 | 2023-03-28 | 松下知识产权经营株式会社 | 锂二次电池用正极和锂二次电池 |
US20220376261A1 (en) * | 2019-07-01 | 2022-11-24 | Daikin Industries, Ltd. | Composition for electrochemical device, positive electrode mixture, positive electrode structure, and secondary battery |
Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998005083A1 (fr) * | 1996-07-30 | 1998-02-05 | Sony Corporation | Cellule electrolytique secondaire non aqueuse |
JPH10312792A (ja) * | 1997-05-12 | 1998-11-24 | Toyota Central Res & Dev Lab Inc | リチウム二次電池用正極電極およびその製造方法 |
JPH10324758A (ja) | 1997-03-26 | 1998-12-08 | Sumitomo Chem Co Ltd | パラアラミド系多孔質フィルムおよびそれを用いた電池用セパレーターとリチウム二次電池 |
JPH1140140A (ja) | 1997-07-23 | 1999-02-12 | Asahi Chem Ind Co Ltd | 非水系二次電池 |
JP2000030686A (ja) | 1998-04-27 | 2000-01-28 | Sumitomo Chem Co Ltd | 非水電解質電池セパレ―タ―とリチウム二次電池 |
JP2005050582A (ja) * | 2003-07-30 | 2005-02-24 | Mitsubishi Chemicals Corp | リチウム二次電池用正極及びそれを用いたリチウム二次電池 |
JP2006092808A (ja) * | 2004-09-21 | 2006-04-06 | Nissan Motor Co Ltd | 電池構造体 |
JP2006172887A (ja) * | 2004-12-15 | 2006-06-29 | Nissan Motor Co Ltd | 電池用電極の製造方法 |
JP2006253450A (ja) * | 2005-03-11 | 2006-09-21 | Nisshinbo Ind Inc | 電極用組成物、蓄電デバイス用電極および蓄電デバイス |
JP2006278303A (ja) * | 2005-03-25 | 2006-10-12 | Nippon Zeon Co Ltd | 非水電解質二次電池電極用バインダー、バインダー組成物、電極用組成物、ならびに電極 |
JP2008084826A (ja) | 2006-04-21 | 2008-04-10 | Sumitomo Chemical Co Ltd | 正極用粉末および正極合剤 |
JP2008117541A (ja) * | 2006-10-31 | 2008-05-22 | Toshiba Corp | 電極の製造方法及び非水電解質電池の製造方法 |
JP2008269890A (ja) * | 2007-04-18 | 2008-11-06 | Nissan Motor Co Ltd | 非水電解質二次電池用電極 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004335192A (ja) * | 2003-05-02 | 2004-11-25 | Sony Corp | 正極の製造方法および電池の製造方法 |
JP4929674B2 (ja) * | 2004-10-27 | 2012-05-09 | 住友化学株式会社 | 球状ニッケル酸リチウム粒子の製造方法および球状の複合酸化物粒子の製造方法 |
WO2009031619A1 (ja) * | 2007-09-04 | 2009-03-12 | Mitsubishi Chemical Corporation | リチウム遷移金属系化合物粉体、その製造方法及びその焼成前駆体となる噴霧乾燥体、並びに、それを用いたリチウム二次電池用正極及びリチウム二次電池 |
-
2009
- 2009-09-28 JP JP2009222134A patent/JP2011070994A/ja active Pending
-
2010
- 2010-09-24 US US13/498,274 patent/US20120183850A1/en not_active Abandoned
- 2010-09-24 EP EP10818873.1A patent/EP2485303A4/en not_active Withdrawn
- 2010-09-24 KR KR1020127007271A patent/KR20120081982A/ko not_active Application Discontinuation
- 2010-09-24 WO PCT/JP2010/066586 patent/WO2011037201A1/ja active Application Filing
- 2010-09-24 CN CN2010800428122A patent/CN102576862A/zh active Pending
Patent Citations (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998005083A1 (fr) * | 1996-07-30 | 1998-02-05 | Sony Corporation | Cellule electrolytique secondaire non aqueuse |
JPH10324758A (ja) | 1997-03-26 | 1998-12-08 | Sumitomo Chem Co Ltd | パラアラミド系多孔質フィルムおよびそれを用いた電池用セパレーターとリチウム二次電池 |
JPH10312792A (ja) * | 1997-05-12 | 1998-11-24 | Toyota Central Res & Dev Lab Inc | リチウム二次電池用正極電極およびその製造方法 |
JPH1140140A (ja) | 1997-07-23 | 1999-02-12 | Asahi Chem Ind Co Ltd | 非水系二次電池 |
JP2000030686A (ja) | 1998-04-27 | 2000-01-28 | Sumitomo Chem Co Ltd | 非水電解質電池セパレ―タ―とリチウム二次電池 |
JP2005050582A (ja) * | 2003-07-30 | 2005-02-24 | Mitsubishi Chemicals Corp | リチウム二次電池用正極及びそれを用いたリチウム二次電池 |
JP2006092808A (ja) * | 2004-09-21 | 2006-04-06 | Nissan Motor Co Ltd | 電池構造体 |
JP2006172887A (ja) * | 2004-12-15 | 2006-06-29 | Nissan Motor Co Ltd | 電池用電極の製造方法 |
JP2006253450A (ja) * | 2005-03-11 | 2006-09-21 | Nisshinbo Ind Inc | 電極用組成物、蓄電デバイス用電極および蓄電デバイス |
JP2006278303A (ja) * | 2005-03-25 | 2006-10-12 | Nippon Zeon Co Ltd | 非水電解質二次電池電極用バインダー、バインダー組成物、電極用組成物、ならびに電極 |
JP2008084826A (ja) | 2006-04-21 | 2008-04-10 | Sumitomo Chemical Co Ltd | 正極用粉末および正極合剤 |
JP2008117541A (ja) * | 2006-10-31 | 2008-05-22 | Toshiba Corp | 電極の製造方法及び非水電解質電池の製造方法 |
JP2008269890A (ja) * | 2007-04-18 | 2008-11-06 | Nissan Motor Co Ltd | 非水電解質二次電池用電極 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2485303A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113546569A (zh) * | 2021-08-03 | 2021-10-26 | 广东特顺能源设备有限公司 | 一种电池生产专用设备搅拌机 |
Also Published As
Publication number | Publication date |
---|---|
US20120183850A1 (en) | 2012-07-19 |
JP2011070994A (ja) | 2011-04-07 |
CN102576862A (zh) | 2012-07-11 |
KR20120081982A (ko) | 2012-07-20 |
EP2485303A4 (en) | 2013-09-11 |
EP2485303A1 (en) | 2012-08-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5640311B2 (ja) | リチウム複合金属酸化物および非水電解質二次電池 | |
JP5287520B2 (ja) | 電極活物質、電極および非水電解質二次電池 | |
WO2011037201A1 (ja) | 正極合剤、正極および非水電解質二次電池 | |
JP5644392B2 (ja) | 遷移金属複合水酸化物およびリチウム複合金属酸化物 | |
JP5842478B2 (ja) | リチウム複合金属酸化物およびその製造方法 | |
JP5531602B2 (ja) | 電極活物質、電極および非水電解質二次電池 | |
JP2010021134A (ja) | リチウム複合金属酸化物の製造方法 | |
JP5504800B2 (ja) | リチウム複合金属酸化物および正極活物質 | |
JP5682151B2 (ja) | 遷移金属複合水酸化物およびリチウム複合金属酸化物 | |
WO2010143641A1 (ja) | 電極合剤、電極合剤ペースト、電極および非水電解質二次電池 | |
JP5699436B2 (ja) | 層状構造リチウム複合金属酸化物の製造方法 | |
WO2011016574A1 (ja) | 粉末材料および正極合剤 | |
JP5487821B2 (ja) | リチウム複合金属酸化物および正極活物質 | |
JP5381330B2 (ja) | 電極合剤、電極および非水電解質二次電池 | |
JP5780059B2 (ja) | 正極活物質、正極および非水電解質二次電池 | |
JP5742192B2 (ja) | リチウム複合金属酸化物の製造方法 | |
WO2012029673A1 (ja) | 正極活物質 | |
JP5771891B2 (ja) | 導電性正極活物質粉末の製造方法 | |
JP5742193B2 (ja) | リチウム複合金属酸化物および非水電解質二次電池 | |
JP2011153067A (ja) | 複合金属水酸化物およびリチウム複合金属酸化物の製造方法ならびに非水電解質二次電池 | |
JP5515435B2 (ja) | リチウムニッケル複合金属酸化物用原料粉末 | |
JP2010118161A (ja) | 非水電解質二次電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201080042812.2 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 10818873 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20127007271 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13498274 Country of ref document: US Ref document number: 2751/CHENP/2012 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2010818873 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |