WO2016121156A1 - 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池 - Google Patents

非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池 Download PDF

Info

Publication number
WO2016121156A1
WO2016121156A1 PCT/JP2015/075062 JP2015075062W WO2016121156A1 WO 2016121156 A1 WO2016121156 A1 WO 2016121156A1 JP 2015075062 W JP2015075062 W JP 2015075062W WO 2016121156 A1 WO2016121156 A1 WO 2016121156A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
electrolyte secondary
electrode material
secondary battery
lithium
Prior art date
Application number
PCT/JP2015/075062
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
誠之 廣岡
山田　將之
智仁 関谷
Original Assignee
日立マクセル株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日立マクセル株式会社 filed Critical 日立マクセル株式会社
Publication of WO2016121156A1 publication Critical patent/WO2016121156A1/ja

Links

Images

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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • 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
    • 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 material for a non-aqueous electrolyte secondary battery, a manufacturing method thereof, and a non-aqueous electrolyte secondary battery.
  • non-aqueous electrolyte secondary batteries mounted on portable electronic devices such as mobile phones and notebook computers are required to have a higher capacity in order to ensure a longer driving time.
  • Patent Document 1 a lithium ion battery using high lithium-containing transition metal oxide particles as a positive electrode material has a crystal structure from the central portion of the positive electrode material toward the outermost surface portion. It is proposed that the battery characteristics such as load characteristics, discharge capacity, and charge / discharge efficiency in high voltage charge / discharge as high as 4.8V based on Li can be improved by gradually changing the layer structure from the layered rock salt structure to the spinel structure. Has been.
  • Patent Document 2 in a lithium ion battery using Li-containing cobalt oxide particles as a positive electrode material, by reducing only the outermost surface of the positive electrode material, It has been reported that deterioration due to a room temperature charge / discharge cycle at a charge end voltage of 4.4 V on the basis of Li can be suppressed.
  • the lithium ion battery using the high lithium-containing transition metal oxide particles described in Patent Document 1 as a positive electrode material can be increased in capacity by high-voltage charging, but other Li-containing transitions have a large Li-containing capacity. True density is lower than metal oxide.
  • the average charge / discharge potential is low, there is a problem that it is difficult to improve the energy density per volume and the output density.
  • the lithium ion battery using the lithium-containing cobalt oxide particles described in Patent Document 2 as a positive electrode material has a high true density and a high potential in a wide range of charged states, it has a high charge end voltage. By charging and discharging, high energy and high output can be expected. However, by continuing to maintain a high voltage in a high temperature environment, Co elution is promoted, resulting in a problem that the positive electrode material is structurally broken.
  • the present invention provides a positive electrode material for a non-aqueous electrolyte secondary battery that can suppress the elution of Co in a high temperature environment while improving the energy density per volume and the output density by increasing the charge end voltage. It is an object of the present invention to provide a non-aqueous electrolyte secondary battery using the manufacturing method and the positive electrode material.
  • the present inventors conducted extensive research and found that the problem is solved by making the outermost surface of lithium-containing cobalt oxide particles having a predetermined composition a specific structure.
  • the gist of the present invention is as follows.
  • M is Ni, Mn, Al, Mg, Zr, V, W, Mo, Cr, Bi, Cu, Ti, Si
  • the particles are further coated with an oxide or fluoride containing one or more elements selected from the group consisting of Li, Zr, Ti, Al, Mg, Ni, Mn, Zn, and P;
  • oxide or fluoride containing one or more elements selected from the group consisting of Li, Zr, Ti, Al, Mg, Ni, Mn, Zn, and P;
  • a method for producing a positive electrode material for a nonaqueous electrolyte secondary battery according to (1) above Mixing Li 2 CO 3 and / or LiOH with a lithium-containing cobalt oxide raw material; And a step of performing an annealing treatment within a temperature range of 950 ° C. to 1100 ° C. for 5 hours to 48 hours.
  • a non-aqueous electrolyte secondary battery comprising a positive electrode including the positive electrode material for a non-aqueous electrolyte secondary battery according to any one of (1) to (3), a negative electrode, a separator, and a non-aqueous electrolyte.
  • the positive electrode has a general composition formula Li 1 + a Ni 1-bcd Co b Mn c M ′ d O 2-e (wherein M ′ is selected from the group consisting of Al, Mg, Zr, V, W, Mo, Cr, Ti, B, Si, Fe, P, F, S and Cl)
  • M ′ is selected from the group consisting of Al, Mg, Zr, V, W, Mo, Cr, Ti, B, Si, Fe, P, F, S and Cl
  • M ′ is selected from the group consisting of Al, Mg, Zr, V, W, Mo, Cr, Ti, B, Si, Fe, P, F, S and Cl
  • the lithium-containing nickel / cobalt / manganese oxide represented by 01) is in a proportion of 5% by mass or more and 50% by mass or less based on the total of the lithium-containing nickel / cobalt / manganese oxide and the lithium-containing cobalt oxide.
  • the positive electrode material for a non-aqueous electrolyte secondary battery is General composition formula Li 1 + x Co 1-y M y O 2- ⁇ (1)
  • M is one or more selected from the group consisting of Ni, Mn, Al, Mg, Zr, V, W, Mo, Cr, Bi, Cu, Ti, Si, Fe, P, F and Cl Element containing particles containing lithium-containing cobalt oxide represented by 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.1, and 0 ⁇ ⁇ ⁇ 0.02. It has a spinel structure.
  • the outermost surface of the particle refers to a region having a thickness within 100 nm of the surface portion of the particle.
  • a positive electrode mixture slurry in which the positive electrode material is dispersed in a solvent together with a binder, a conductive auxiliary agent, and the like is prepared. Can be applied to the surface of the positive electrode current collector to form a positive electrode mixture layer.
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention is in the form of particles, is composed of secondary particles in which the primary particles are aggregated, or primary particles, and each shape may be substantially spherical.
  • the above shape can be confirmed by observing particles existing in a predetermined region with a scanning electron microscope.
  • the diameter of the particles is preferably in the range of 5 ⁇ m to 50 ⁇ m, more preferably distributed so as to have peaks in the range of 5 ⁇ m to 15 ⁇ m and in the range of 20 ⁇ m to 50 ⁇ m. By having a plurality of peaks, the packing state of the particles in the positive electrode mixture layer is improved.
  • the particle size distribution can be measured by a laser diffraction / scattering particle size distribution measuring apparatus.
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention needs to reduce the interface with the non-aqueous electrolyte from the viewpoint of suppressing Co elution. Therefore, it is advantageous to have a small BET specific surface area. However, if the BET specific surface area of the particles is too small, the density at the time of stacking will be small, so that the battery capacity will be reduced and the discharge characteristics at high load will be reduced. Problem arises. For this reason, it is preferable that the BET specific surface area S is in the range of 0.01 ⁇ S ⁇ 1.0 [m 2 / g].
  • the BET specific surface area can be obtained by measuring the surface area using the BET formula, which is a theoretical formula for multimolecular layer adsorption. Specifically, the BET specific surface area can be obtained using a specific surface area measuring apparatus by a nitrogen adsorption method.
  • x related to Li is 0 ⁇ x ⁇ 0.1, and more preferably 0 ⁇ x ⁇ 0.03.
  • x is less than 0, the particles of the positive electrode material become small, and the diameter of the particles is less than 5 ⁇ m.
  • the density is small, and thus a sufficient battery capacity cannot be obtained.
  • the surface area is increased, Co elution is likely to occur.
  • x exceeds 0.1, a large amount of oxygen deficiency occurs. For this reason, the potential in the low charge state is lowered, and the output is lowered in the low charge state.
  • the oxygen is deficient, the structure is easily collapsed and the cycle life is shortened. Furthermore, since there is a large amount of lithium on the particle surface of the positive electrode material, the positive electrode mixture slurry prepared using such a positive electrode material becomes a gel, and the resistance of the formed positive electrode mixture layer is increased, or during the battery reaction. This is not preferable because gas is generated.
  • X in relation to Li is in the range of 0 ⁇ x ⁇ 0.1 means that Li is slightly in excess of the stoichiometric composition. In such a state, a phase transition phenomenon accompanied by structural collapse at a high voltage of 4.5 V or higher is suppressed, and Co elution is prevented.
  • the average valence of Co in the positive electrode material is preferably 2.8 or more and 3.3 or less.
  • the valence of Co is calculated from inductively coupled plasma emission analysis and iodometric titration, and can be obtained by quantifying the atomic ratio of Li and Co and the amount of oxygen.
  • y related to M (Ni, Mn, Al, Mg, Zr, V, W, Mo, Cr, Bi, Cu, Ti, Si, Fe, P, F, and Cl) is 0. ⁇ y ⁇ 0.1.
  • Ni, Mn, Al, Mg, Zr, V, W, Mo, Cr, Bi, Cu, and Ti various battery characteristics can be improved by replacing part of Co.
  • Si, Fe, P, F, Cl, etc. may be inevitably contained as impurities.
  • Ni is preferable to add Ni as M because the effect of suppressing Co elution is increased. Although other element substitution can stabilize the structure of the lithium-containing cobalt oxide and suppress the Co elution, there is a problem that the charge / discharge capacity decreases. On the other hand, if Ni is within the range of the present invention, the change in charge / discharge capacity due to the increase / decrease of the addition amount is extremely small, and Ni is preferable as an additive element for suppressing Co elution while maintaining the battery at a high capacity.
  • the addition amount y of Ni is preferably 0 ⁇ y ⁇ 0.1, and more preferably 0 ⁇ y ⁇ 0.05 in order to suppress a decrease in potential.
  • the added amount y of Mg is 0 ⁇ y ⁇ 0.1.
  • Addition of Al as M has almost the same ionic radius of 6-coordinate Co ions and Al ions, so it is replaced with Co sites to stabilize the structure of lithium-containing cobalt oxides and elution of Co There is an effect to suppress. Moreover, there exists an effect which improves heat resistance. However, like Mg, if added excessively, the crystal lattice of the lithium-containing cobalt oxide is distorted, which may cause a decrease in battery capacity and a decrease in load characteristics due to a decrease in Li mobility.
  • the addition amount y of Al is preferably 0 ⁇ y ⁇ 0.1, and more preferably 0 ⁇ y ⁇ 0.01.
  • the addition of Zr has the effect of improving the high-voltage charge / discharge cycle life at 4.3 V or higher in addition to the effect of increasing the potential in the low charge state and improving the output.
  • the amount y of Zr is preferably 0 ⁇ y ⁇ 0.1, and more preferably 0.001 ⁇ y ⁇ 0.005. When it exceeds 0.005, the growth of the positive electrode material particles is suppressed, and the particles may be small. When such a small particle is used to form the positive electrode mixture layer, there is a possibility that sufficient battery capacity cannot be obtained due to its low density. Further, since the surface area is increased, Co elution is likely to occur. Mn, V, W, Mo, Cr, Ti, and the like can exhibit the same effects as Zr.
  • the addition of Bi promotes grain growth and has an effect of suppressing the Co elution reaction even at a high voltage.
  • the amount y of Bi is particularly preferably 0.001 ⁇ y ⁇ 0.005. If it exceeds 0.005, a heterogeneous phase appears and the electrochemical characteristics may be deteriorated.
  • ⁇ related to oxygen is 0 ⁇ ⁇ ⁇ 0.02.
  • the collapse of the crystal structure due to the desorption of oxygen is considered to be one cause of Co elution. If ⁇ calculated from iodometric titration and ICP is 0.02 or less, oxygen deficiency is sufficiently small.
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention has a layered rock salt structure in which the central part of the lithium-containing cobalt oxide particles represented by the general composition formula (1) belongs to the space group R3-m.
  • the presence of a structure-stable spinel structure in the outermost shell suppresses deterioration of the surface of the lithium-containing cobalt oxide particles due to a disproportionation reaction or a side reaction with an electrolytic solution such as Co elution by reduction.
  • the As a result the continuous charging characteristics at high temperature and high voltage are dramatically improved.
  • the Raman spectrum of the particle surface of the lithium-containing cobalt oxide effect is obtained, having a shoulder peak in the range of 650cm -1 ⁇ 700cm -1.
  • the shoulder peak has a left-right asymmetric peak shape at about 590 cm ⁇ 1 in the Raman spectrum, and a spectral intensity higher than the background is maintained between 700 cm ⁇ 1 from the peak top.
  • An example of a Raman spectrum measurement method is as follows. A laser beam having a wavelength of 532 nm and an intensity of 0.7 mW to 1.0 mW is irradiated to one point on the particle surface of lithium-containing cobalt oxide, and the generated Raman scattered light is detected by a CCD. Can be obtained.
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention is an oxidation in which particles contain one or more elements selected from the group consisting of Li, Zr, Ti, Al, Mg, Ni, Mn, Zn, and P. It may be further coated with a product or fluoride. In this case, in addition to improving the deterioration suppressing effect due to the charge / discharge cycle, the Co elution suppressing effect is also improved. However, if the amount of oxide or fluoride to be coated is too large, the resistance may increase and the battery capacity may decrease. Therefore, the element contained in the oxide or fluoride to be coated is preferably 10% or less of the number of molecules of the lithium-containing cobalt oxide represented by the general composition formula (1).
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention can be produced, for example, by firing a mixture powder in which a Li compound, a Co compound, an M compound, and the like are mixed at an appropriate ratio.
  • a precursor hydroxide excluding Li obtained by a coprecipitation method or the like with a Li compound and baking.
  • Li compound LiOH, Li 2 CO 3, LiCl, or the like can be used.
  • Co compound and the M compound hydroxides or oxides of these elements can be used.
  • the temperature during synthesis is 800 ° C. to 1100 ° C.
  • the temperature holding time is 5 hours to 48 hours
  • the heating / cooling rate r is 1 ⁇ r ⁇ 5 ° C./min
  • the atmosphere during synthesis is air or oxygen atmosphere. Is preferred.
  • the lithium-containing cobalt oxide after combining, mixing Li 2 CO 3 and / or LiOH. It is preferable to mix at a molecular weight ratio of 0.5% to 10%.
  • annealing is performed at a temperature range of 950 ° C. to 1100 ° C. for 2 hours to 20 hours.
  • the heating / cooling rate r is preferably 1 ⁇ r ⁇ 5 ° C./min
  • the atmosphere during annealing is an air or oxygen atmosphere
  • the pressure is preferably atmospheric pressure or lower.
  • the outermost surface of the particle can be formed into a spinel structure by performing an annealing treatment within a temperature range of 950 ° C. to 1100 ° C. for 5 hours to 48 hours.
  • the heating / cooling rate r is preferably 1 ⁇ r ⁇ 5 ° C./min.
  • the above-described annealing treatment evaporates lithium and oxygen on the surface of the lithium-containing cobalt oxide to form a spinel structure.
  • the oxygen concentration when the oxygen concentration is low, oxygen desorption easily occurs when the amount of Li addition is large. Moreover, when Ni was used as M, it turned out that Ni is easy to transfer to Li site partially.
  • the oxygen concentration can be adjusted as appropriate according to the contents of Li and Ni.
  • x related to Li in the general composition formula (1) is 0.1
  • y related to Ni is 0.05.
  • the oxygen concentration is preferably 20% or more.
  • the ratio of the diffraction intensity attributed to the (003) plane to the diffraction intensity is 1.5 to 30.
  • the particles are oxidized containing at least one element selected from the group consisting of Li, Zr, Ti, Al, Mg, Ni, Mn, Zn, and P.
  • the following procedure is used.
  • a coprecipitate such as Ni and Mn
  • the positive electrode material powder to which the coprecipitate is adhered and the aqueous solution are separated by suction filtration, washed with ultrapure water, and dried.
  • a positive electrode material for a non-aqueous electrolyte secondary battery in which a coating layer of Zr, Ti, Al, Ni, Mn, and Zn oxide is formed can be obtained.
  • an alkoxide of a desired element is dissolved in an alcohol solvent, and is stirred and dried at a temperature of 60 ° C. or higher and 80 ° C. or lower.
  • any of the above methods may be used to coat the surface of the particles of the positive electrode material for a non-aqueous electrolyte secondary battery. After attaching the precursor, LiOH or Li 2 CO 3 may be mixed and fired.
  • a non-aqueous electrolyte solution is added in an aqueous solution of sodium hydroxide or lithium hydroxide adjusted to a pH value of 9 to 11 and a temperature of 60 ° C. to 80 ° C.
  • the powder of the positive electrode material for the next battery is stirred and dispersed, and then aluminum nitride hydrate is added.
  • Ammonium fluoride aqueous solution is dripped little by little, and after stirring for 5 hours or more, it may be filtered, dried, and fired in an inert gas atmosphere.
  • the firing temperature at the time of coating is preferably 400 ° C. or more and 600 ° C. or less, and the firing time is preferably 5 hours or more and 24 hours or less.
  • the firing atmosphere is preferably an oxidizing atmosphere such as air or oxygen when obtaining an oxide, and an inert atmosphere such as nitrogen when obtaining a fluoride.
  • the positive electrode material is mixed with a binder, a conductive auxiliary agent, etc., and dispersed in a solvent to prepare a positive electrode mixture slurry.
  • the mixture slurry is applied to the surface of the positive electrode current collector to form a positive electrode mixture layer.
  • any one of a thermoplastic resin and a thermosetting resin may be used as long as it is chemically stable in the nonaqueous electrolyte secondary battery.
  • a thermoplastic resin and a thermosetting resin may be used as long as it is chemically stable in the nonaqueous electrolyte secondary battery.
  • any inorganic material or organic material may be used as long as it is chemically stable in the nonaqueous electrolyte secondary battery.
  • graphite such as natural graphite and artificial graphite, single- or multi-walled carbon nanotubes, graphene, fullerene, VGCF, acetylene black, ketjen black (trade name), carbon such as channel black, furnace black, lamp black, thermal black, etc.
  • Conductive fiber such as black, carbon fiber, metal fiber, metal powder such as aluminum powder, conductive whisker made of carbon fluoride, zinc oxide, potassium titanate, conductive metal oxide such as titanium oxide, polyphenylene derivative, etc.
  • the organic conductive material or the like can be used. These may be used alone or in combination of two or more. Among these, graphite having high conductivity and carbon black excellent in liquid absorption are preferable.
  • the form of the conductive auxiliary agent for example, when it is in the form of particles, it is not limited to only the primary particles, and those having the form of aggregates such as secondary particles and chain structures can also be used. In the case of a conductive additive having such an aggregate form, it is easier to handle and the productivity of the positive electrode can be increased.
  • the mass of the positive electrode material in the positive electrode mixture layer is preferably 85% to 99%. If the content ratio of the positive electrode material is less than 85%, the battery capacity becomes small. Conversely, if the content ratio is more than 99%, the amount of the conductive auxiliary agent is relatively small and the resistance of the positive electrode may be increased.
  • the positive electrode material only the positive electrode material for the non-aqueous electrolyte secondary battery represented by the general formula (1) may be used, but may be combined with other positive electrode materials.
  • the positive electrode material to be combined include, for example, the general composition formula Li 1 + a Ni 1-bcd Co b Mn c M ′ d O 2-e (2) (Wherein M ′ is one or more elements selected from the group consisting of Al, Mg, Zr, V, W, Mo, Cr, Ti, B, Si, Fe, P, F, S and Cl.
  • Lithium-containing nickel-cobalt-manganese oxides When combining the lithium-containing nickel / cobalt / manganese oxide, the lithium-containing nickel / cobalt / manganese oxide and the lithium-containing cobalt oxide are preferably contained in a proportion of 5% by mass or more and 50% by mass or less.
  • the electrochemical characteristics and safety as a non-aqueous electrolyte secondary battery can be improved.
  • the mass of the binder in the positive electrode mixture layer is preferably 0.2% by mass to 5% by mass.
  • the mass of the conductive additive in the positive electrode mixture layer is preferably 0.5% by mass to 8% by mass.
  • a positive electrode material mixture including a positive electrode material for a nonaqueous electrolyte secondary battery according to the present invention as a positive electrode material, a binder and a conductive auxiliary agent is dispersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) or the like.
  • NMP N-methyl-2-pyrrolidone
  • a positive electrode mixture slurry is prepared. After this positive electrode mixture slurry is applied to one or both surfaces of the positive electrode current collector, NMP is evaporated, and a press treatment is performed to form a positive electrode mixture layer on the current collector surface.
  • the press treatment is for adjusting the thickness and density of the positive electrode mixture layer, and can be performed using, for example, a roll press machine or a hydraulic press machine.
  • the density of the positive electrode mixture layer produced in this way is preferably 3.5 g / cm 3 or more and 4.5 g / cm 3 or less.
  • the method for manufacturing the positive electrode is not limited to the above, and other manufacturing methods may
  • the material of the positive electrode current collector is not particularly limited as long as it is a chemically stable electron conductor in the non-aqueous electrolyte secondary battery.
  • the material of the positive electrode current collector is not particularly limited as long as it is a chemically stable electron conductor in the non-aqueous electrolyte secondary battery.
  • aluminum, aluminum alloy, stainless steel, nickel, titanium, carbon, conductive resin, etc. aluminum, aluminum alloy, a composite material in which a carbon layer or a titanium layer is formed on the surface of stainless steel, or the like can be used. .
  • aluminum or aluminum alloy is preferable because it is lightweight and has high conductivity.
  • the positive electrode current collector for example, a foil, a film, a sheet, a net, a punching sheet, a lath body, a porous body, a foamed body, a molded body of a fiber group, or the like of the above materials can be used. Further, the surface of the positive electrode current collector can be roughened by surface treatment.
  • the thickness of the positive electrode current collector is not particularly limited, but is preferably 1 ⁇ m to 500 ⁇ m.
  • the nonaqueous electrolyte secondary battery according to the present invention has a positive electrode using the positive electrode material for a nonaqueous electrolyte secondary battery according to the present invention as a positive electrode material. There are no particular restrictions on the configuration and structure other than the positive electrode.
  • the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention is less likely to transition to CoO 2 (O1 structure).
  • a non-aqueous electrolyte secondary battery using a lithium metal as a negative electrode and a positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention as a positive electrode charging to 5 V at 0.1 C or less at room temperature, In the dQ / dV curve obtained by differentiating the charge curve of the positive electrode at this time, the peak potential due to the start of the phase transition to the O1 structure that appears on the highest potential side is 4.64 V or higher. . This indicates that the positive electrode material for a non-aqueous electrolyte secondary battery according to the present invention is not easily transferred to CoO 2 (O1 structure).
  • Example 1 ⁇ Synthesis of positive electrode material> Li 2 CO 3 as the Li compound and Co 3 O 4 as the Co compound were mixed in a mortar at an appropriate mixing ratio, then solidified into a pellet shape, and using a muffle furnace in an atmospheric atmosphere at atmospheric pressure, Heat treatment was performed at 950 ° C. for 24 hours.
  • Li 2 CoO 3 is added to the lithium-containing cobalt oxide by 1.5% in a molecular weight ratio, mixed using a mortar, and in an oxygen gas atmosphere (oxygen) using a tubular electric furnace.
  • a positive electrode for a non-aqueous electrolyte secondary battery comprising lithium-containing cobalt oxide particles represented by the general composition formula LiCoO 2 by performing an annealing treatment at 1000 ° C. for 10 hours at a gas flow rate of 0.5 L / min) The material was synthesized.
  • the composition was measured by an ICP (Inductivity Coupled Plasma) method and an iodometric titration method.
  • the particle size was measured with a laser diffraction / scattering particle size distribution analyzer, and it was confirmed that the average diameter was 20 ⁇ m.
  • the specific surface area was 0.15 m ⁇ 2 > / g.
  • the Raman spectrum of the positive electrode material for a non-aqueous electrolyte secondary battery according to Example 1 was measured by irradiating a point on the particle surface with laser at a wavelength of 532 nm, an intensity of 0.8 mW, and an irradiation time of 30 seconds.
  • a shoulder peak was confirmed in the range of 650cm -1 ⁇ 700cm -1. It is considered that a shoulder peak as shown in FIG. 1 appears as a result of overlapping spectra of LT-LiCoO 2 and Co 3 O 4 having a spinel structure, and it was confirmed that a spinel structure exists.
  • the X-ray diffraction of the positive electrode material for nonaqueous electrolyte secondary batteries according to Example 1 was measured. From the X-ray diffraction measurement result shown in FIG. 2, it was a layered rock salt structure belonging to the space group R3-m, and no heterogeneous phase was confirmed. This suggests that the spinel structure confirmed by the Raman spectrum does not have long-range order and exists in a state having lattice strain on the outermost surface of the particle.
  • a lithium-containing cobalt oxide powder of the above general composition formula LiCoO 2 was dispersed in an NMP solution containing PVDF as a binder to prepare a mixed solution.
  • the mass of PVDF in the mass of the NMP solution is 10%.
  • the mass ratio of the lithium-containing cobalt oxide having the above composition and the NMP solution was 95: 5.
  • 2.5 parts by mass of carbon black as a conductive assistant was added, kneaded in a mortar, and NMP was added to adjust the viscosity to prepare a positive electrode mixture slurry.
  • the positive electrode mixture slurry was applied to a positive electrode current collector made of aluminum foil having a thickness of 15 ⁇ m using a baker-type applicator, and then dried at 80 ° C. for 1 hour. An agent layer was formed.
  • the positive electrode current collector on which the positive electrode mixture layer was formed was processed into a disk shape having a diameter of 15 mm, then pressed at a pressure of about 30 MPa, and further dried at 100 ° C. for 20 hours in a vacuum dryer. A positive electrode was produced by such a process.
  • a metal lithium rolled plate having a predetermined thickness was processed into a disk shape having a diameter of 16 mm to produce a negative electrode.
  • Nonaqueous electrolyte was prepared by dissolving lithium hexafluorophosphate (LiPF 6 ) at a molar concentration (mol / l) in a solvent in which ethylene carbonate and diethyl carbonate having a volume ratio of 1: 2 were mixed. .
  • LiPF 6 lithium hexafluorophosphate
  • FIG. 3 schematically shows a cross section of the assembled nonaqueous electrolyte secondary battery 1. The assembly was performed as follows.
  • the separator 3 After the insulating ring 8 was inserted into the side surface of the stainless steel container 13, the negative electrode 4, the separator 3, and the positive electrode 2 were laminated in this order, and the nonaqueous electrolyte was impregnated into the separator 3.
  • a microporous film made of polypropylene was used as the separator 3.
  • An aluminum pressing plate 5 and a leaf spring 6 are sequentially stacked on the positive electrode 2, a stainless steel lid 7 is placed via an insulating packing 9, and tightened with a bolt 12 and a nut 11 via an insulating sleeve 10, A flat battery was constructed.
  • the positive electrode 2 is electrically connected to the lid 7 via the holding plate 5 and the leaf spring 6, and the negative electrode 4 is electrically connected to the bolt 12 via the container 13. Thereby, electrical energy can be taken out from the inside of the battery using the lid 7 and the bolt 12 as terminals.
  • a positive electrode material composed of lithium-containing cobalt oxide particles represented by the general composition formula LiCoO 2 was synthesized as a positive electrode material by heat treatment at 1000 ° C. for 20 hours. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 2 was fabricated in the same procedure as in Example 1 above.
  • Example 3 The annealing conditions of Example 1 were changed, Li 2 CoO 3 was added at a molecular weight ratio of 10%, mixed using a mortar, and in an oxygen gas atmosphere using a tubular electric furnace (oxygen gas flow rate 0.5 L / min) Then, a positive electrode material composed of lithium-containing cobalt oxide particles represented by a general composition formula Li 1.05 CoO 1.98 was synthesized as a positive electrode material by performing heat treatment at 1000 ° C. for 10 hours. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 3 was fabricated in the same procedure as in Example 1 above.
  • Example 4 Lithium represented by the general composition formula LiCo 0.95 Ni 0.05 O 2 as the positive electrode material is the same as that of Example 1 except that Ni (OH) 2 is added to Example 1 as the Ni compound. Containing cobalt oxide was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 4 was fabricated in the same procedure as in Example 1 above.
  • Example 5 A lithium-containing cobalt oxide represented by the general composition formula LiCo 0.98 Ni 0.02 O 2 was synthesized as a positive electrode material in the same procedure as in Example 4. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 5 was fabricated in the same procedure as in Example 1 above.
  • Example 6 Instead of the Ni compound used in Example 4, Mg (OH) 2 was used as the Mg compound, and the general composition formula LiCo 0.99 Mg 0.01 O was used as the positive electrode material in the same procedure as in Example 1 except that. A lithium-containing cobalt oxide represented by 2 was synthesized. Using this positive electrode material, a non-aqueous electrolyte secondary battery according to Example 6 was fabricated in the same procedure as in Example 1 above.
  • Example 7 Instead of the Ni compound used in Example 4, Al (OH) 3 was used as the Al compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.97 Al was used as the positive electrode material. A lithium-containing cobalt oxide represented by 0.03 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 7 was fabricated in the same procedure as in Example 1 above.
  • Example 8 instead of the Ni compound used in Example 4, Bi (OH) 2 was used as the Bi compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.995 Bi was used as the positive electrode material. A lithium-containing cobalt oxide represented by 0.005 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 8 was fabricated in the same procedure as in Example 1 above.
  • Example 9 instead of the Ni compound used in Example 4, V 2 O 5 was used as the V compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.97 V 0 was used as the positive electrode material. A lithium-containing cobalt oxide represented by 0.03 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 9 was produced in the same procedure as in Example 1 above.
  • Example 10 instead of the Ni compound used in Example 4, TiO 2 was used as the Ti compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.97 Ti 0.03 was used as the positive electrode material. A lithium-containing cobalt oxide represented by O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 10 was fabricated in the same procedure as in Example 1 above.
  • Example 11 instead of the Ni compound used in Example 4, Mn (OH) 2 was used as the Mn compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.99 Mn was used as the positive electrode material. A lithium-containing cobalt oxide represented by 0.01 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 11 was fabricated in the same procedure as in Example 1 above.
  • Example 12 instead of the Ni compound used in Example 4, ZrO 2 was used as the Zr compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.995 Zr 0.005 was used as the positive electrode material. A lithium-containing cobalt oxide represented by O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 12 was fabricated in the same procedure as in Example 1 above.
  • Example 13 In addition to the Ni compound used in Example 4, Mg (OH) 2 was used as the Mg compound, and the other procedures were the same as in Example 1 except that the general composition formula Li 1.01 Co 0.97 Ni was used as the positive electrode material. A lithium-containing cobalt oxide represented by 0.02 Mg 0.01 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 13 was fabricated in the same procedure as in Example 1 above.
  • Example 14 In addition to the Ni and Mg compounds used in Example 13, ZrO 2 was used as the Zr compound, and the other procedures were the same as in Example 1 except that the general composition formula LiCo 0.965 Ni 0.02 Mg 0 was used as the positive electrode material. A lithium-containing cobalt oxide represented by .01 Zr 0.005 O 2 was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 14 was fabricated in the same procedure as in Example 1 above.
  • Example 15 A lithium-containing cobalt oxide represented by a general composition formula Li 1.01 Co 0.97 Ni 0.02 Mg 0.01 O 2 was synthesized as a positive electrode material in the same procedure as in Example 13. Next, the positive electrode material powder for a nonaqueous electrolyte secondary battery is stirred and dispersed in an aqueous lithium hydroxide solution adjusted to have a pH value of 9 or more and 11 or less and a temperature of 60 ° C. or more and 80 ° C. or less. NO 3) was added dropwise 3 ⁇ 9H 2 O. At this time, Al (OH) 3 coprecipitate was produced by simultaneously dropping ammonia water so that the pH value would not change.
  • Example 16 A lithium-containing cobalt oxide represented by a general composition formula Li 1.01 Co 0.97 Ni 0.02 Mg 0.01 O 2 was synthesized as a positive electrode material in the same procedure as in Example 13. Next, zirconium isopropoxide was dissolved in an isopropyl alcohol solvent, stirred at 60 ° C. for 10 hours together with the positive electrode material powder for a non-aqueous electrolyte secondary battery, and dried at 80 ° C. This powder was fired at 400 ° C. in an air atmosphere for 10 hours.
  • Example 16 Using such a process, an oxide-coated positive electrode material in which the number of Zr atoms in the oxide film formed on the surface of the positive electrode material was 1% of the number of molecules of the lithium-containing cobalt oxide was produced. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Example 16 was produced in the same procedure as in Example 1.
  • Example 17 A lithium-containing cobalt oxide represented by a general composition formula Li 1.01 Co 0.97 Ni 0.02 Mg 0.01 O 2 was synthesized as a positive electrode material in the same procedure as in Example 13. Next, after stirring and dispersing the positive electrode material powder for a non-aqueous electrolyte secondary battery in a lithium hydroxide aqueous solution adjusted to a pH value of 9 or more and 11 or less and a temperature of 60 ° C., aluminum nitride hydrate was added. I put it in. Ammonium fluoride aqueous solution was dropped there little by little, and after stirring for 10 hours or more, suction filtration was performed, followed by washing with ultrapure water, followed by vacuum drying at 80 ° C. for 24 hours.
  • This powder was fired in a nitrogen gas atmosphere for 10 hours.
  • a fluoride-coated positive electrode material in which the number of Al atoms in the AlF 3 coating formed on the surface of the positive electrode material was 1% of the number of molecules of the lithium-containing cobalt oxide was produced.
  • a nonaqueous electrolyte secondary battery according to Example 17 was fabricated in the same procedure as in Example 1.
  • Table 1 lists the compositions of the positive electrode materials of Examples 1 to 17 and the elements covering the surface of the positive electrode material.
  • Comparative Example 1 The annealing treatment conditions were changed from Example 1, Li 2 CoO 3 was added at a molecular weight ratio of 0%, mixed using a mortar, and in an oxygen gas atmosphere using a tubular electric furnace (oxygen gas flow rate 0.5 mL / min) Then, a positive electrode material for a non-aqueous electrolyte secondary battery composed of lithium-containing cobalt oxide particles represented by the general composition formula Li 0.98 CoO 2 is synthesized as a positive electrode material by performing a heat treatment at 1000 ° C. for 10 hours. did. Using this positive electrode material, a non-aqueous electrolyte secondary battery according to Comparative Example 1 was produced in the same procedure as in Example 1.
  • Example 2 The annealing treatment conditions were changed from Example 1, Li 2 CoO 3 was added at a molecular weight ratio of 1.5%, mixed using a mortar, and heat-treated at 1000 ° C. for 10 hours in an air atmosphere using a muffle furnace.
  • a positive electrode material for a non-aqueous electrolyte secondary battery composed of lithium-containing cobalt oxide particles represented by the general composition formula LiCoO 2 was synthesized as a positive electrode material.
  • a nonaqueous electrolyte secondary battery according to Comparative Example 2 was produced in the same procedure as in Example 1.
  • Example 3 The annealing process conditions are changed from Example 1, Li 2 CoO 3 is added at a molecular weight ratio of 6%, mixed using a mortar, and heat-treated at 1000 ° C. for 10 hours in an air atmosphere using a muffle furnace.
  • a positive electrode material for a non-aqueous electrolyte secondary battery composed of lithium-containing cobalt oxide particles represented by the general composition formula Li 1.10 CoO 1.95 was synthesized as a positive electrode material.
  • a non-aqueous electrolyte secondary battery according to Comparative Example 3 was produced in the same procedure as in Example 1.
  • Example 4 Non-water consisting of lithium-containing cobalt oxide particles represented by the general composition formula Li 0.99 Co 0.95 Ni 0.05 O 2 as a positive electrode material, synthesized without carrying out the annealing treatment of Example 4 A positive electrode material for an electrolyte secondary battery was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Comparative Example 4 was produced in the same procedure as in Example 1.
  • Example 5 The annealing treatment conditions of Example 4 were changed, Li 2 CoO 3 was added at a molecular weight ratio of 1.0%, mixed using a mortar, and in an oxygen gas atmosphere using a tubular electric furnace (oxygen gas flow rate 0.5 L / min) ), A non-aqueous solution comprising lithium-containing cobalt oxide particles represented by the general composition formula Li 0.97 Co 0.95 Ni 0.05 O 2 as a positive electrode material by performing a heat treatment at 1000 ° C. for 10 hours. A positive electrode material for an electrolyte secondary battery was synthesized. Using this positive electrode material, a non-aqueous electrolyte secondary battery according to Comparative Example 5 was produced in the same procedure as in Example 1.
  • Example 6 A non-aqueous electrolyte secondary battery composed of lithium-containing cobalt oxide particles represented by the general composition formula LiCo 0.99 Mg 0.01 O 2 as a positive electrode material, synthesized without performing the annealing treatment of Example 6 A positive electrode material was synthesized. Using this positive electrode material, a nonaqueous electrolyte secondary battery according to Comparative Example 6 was produced in the same procedure as in Example 1.
  • Example 7 A non-aqueous electrolyte secondary battery composed of lithium-containing cobalt oxide particles represented by the general composition formula LiCo 0.99 Mg 0.01 O 2 as a positive electrode material, synthesized without performing the annealing treatment of Example 6 A positive electrode material was synthesized. Next, after coating the surface of the positive electrode material with Al oxide in which the number of Al atoms is 1% of the number of lithium-containing cobalt oxide in the same procedure as in Example 15, the same as in Example 1 A nonaqueous electrolyte secondary battery according to Comparative Example 7 was produced according to the procedure.
  • Example 8 Lithium-containing cobalt oxide particles represented by the general composition formula Li 1.01 Co 0.97 Ni 0.02 Mg 0.01 O 2 as a positive electrode material synthesized without carrying out the annealing treatment of Example 13 A positive electrode material for a non-aqueous electrolyte secondary battery was synthesized. Next, after coating the surface of the positive electrode material with Al oxide in which the number of Al atoms is 1% of the number of lithium-containing cobalt oxide in the same procedure as in Example 15, the same as in Example 1 A nonaqueous electrolyte secondary battery according to Comparative Example 8 was produced according to the procedure.
  • Table 1 lists the compositions of the positive electrode materials of Comparative Examples 1 to 8 and the elements covering the surface of the positive electrode material.
  • charging is started at a constant current of 0.2C load factor, charging is performed until the battery voltage reaches 4.5V vs Li / Li + , and then the current is loaded at a constant voltage of 4.5V vs Li / Li +.
  • the battery was charged until the rate reached 0.02C. Thereafter, the battery was left for 1 hour, and discharged at a constant current until the battery voltage reached 2.5 V at a load factor of 0.2 C.
  • the charge / discharge cycle was repeated 50 times, and the discharge capacity at the 50th cycle was compared with the discharge capacity at the first cycle.
  • charging is started at a constant current of a load factor of 0.05 C, charging is performed until the battery voltage becomes 4.5 V vs Li / Li + , and then the current is loaded at a constant voltage of 4.5 V vs Li / Li +
  • the battery charged to a rate of 0.005 C was left in a constant temperature bath at 60 ° C. for 7 days, and then discharged at a constant current until the battery voltage reached 2.5 V at a load factor of 0.05 C.
  • charging is started at a constant current of a load factor of 0.05 C, charging is performed until the battery voltage becomes 4.45 V vs Li / Li + , and then the current is applied at a constant voltage of 4.45 V vs Li / Li +.
  • the battery was charged until it reached 0.005C. Thereafter, the battery was left for 1 hour and discharged at a constant current until the battery voltage reached 2.5 V at a current of 0.05 C load factor.
  • the case where the final discharge capacity of the test was 80% or more of the discharge capacity after initialization was evaluated as ⁇ , and the case where it was less than 80% was evaluated as x.
  • the evaluation results are shown in Table 2.
  • the initial charge / discharge capacity is 188 mAh / g to 189 mAh / g
  • the capacity retention rate after the cycle test is 80 %.
  • the capacity retention after the storage test was 80% or more, but in Comparative Examples 1 and 2, it was less than 80%.
  • Examples 1, 2, and 3 were about four times as long as Comparative Examples 1 and 2. The difference between the results of the storage test and the continuous charging characteristics is considered to be due to a plurality of deterioration modes.
  • the structurally stable spinel structure is the outermost shell. It is considered that the presence of the Co-elution due to disproportionation or reduction due to a side reaction with the electrolytic solution peculiar to the lithium-containing cobalt oxide is suppressed.
  • Example 4 and Comparative Examples 4 and 5 are all nonaqueous electrolyte secondary batteries using a positive electrode material having a composition in which 5% of Co is replaced by Ni. Although there was no difference in the initial charge capacity, cycle characteristics, and storage test results, the continuous charge characteristics were about 4 times better than Comparative Examples 4 and 5 in terms of continuous charge characteristics, reaching 582 hours. Thus, it was found that when Co was partially replaced by Ni, the structural stability of the spinel structure was present in the outermost shell, so that the characteristics could be further improved compared to the case of no substitution.
  • Example 6 and Comparative Example 6 are non-aqueous electrolyte secondary batteries using a positive electrode material having a composition in which 1% of Co is replaced with Mg. Similar to Ni substitution, it was found that even when a part of Co was replaced with Mg, the structural stability of the spinel structure was present in the outermost shell, so that the characteristics could be further improved compared to the case of no substitution.
  • An element M other than Ni and Mg is also effective. As shown in Examples 7 to 12, even when substituted with Al, Bi, V, Ti, Mn, and Zr, a structure-stable spinel structure exists in the outermost shell. As a result, it was found that the characteristics could be further improved as compared with the case of no substitution. Regarding M, the same effect can be obtained by using Cr, Mo, W instead of Mn, V, Ti. Moreover, these elements can also be mixed and used suitably.
  • Examples 13 and 14 are nonaqueous electrolyte secondary batteries using a positive electrode material in which a part of Co is replaced by a plurality of M at a ratio of several percent. In particular, it has been found that the continuous charge characteristics when Ni, Mg and Zr are combined are dramatically improved and exceed 650 hours.
  • the present invention it is possible to provide a non-aqueous electrolyte secondary battery having a high capacity and excellent in continuous charging characteristics at a high voltage at a high temperature.
  • the non-aqueous electrolyte secondary battery according to the present invention having such characteristics is excellent in the Co elution suppressing effect when charged until the positive electrode potential becomes 4.4 V or higher with respect to lithium.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
PCT/JP2015/075062 2015-01-30 2015-09-03 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池 WO2016121156A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-017849 2015-01-30
JP2015017849A JP6611438B2 (ja) 2015-01-30 2015-01-30 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池

Publications (1)

Publication Number Publication Date
WO2016121156A1 true WO2016121156A1 (ja) 2016-08-04

Family

ID=56542795

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/075062 WO2016121156A1 (ja) 2015-01-30 2015-09-03 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池

Country Status (2)

Country Link
JP (1) JP6611438B2 (enrdf_load_stackoverflow)
WO (1) WO2016121156A1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112840487A (zh) * 2018-10-15 2021-05-25 日本化学工业株式会社 锂二次电池用正极活性物质、其制造方法和锂二次电池

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110998931B (zh) * 2017-08-30 2023-04-04 株式会社村田制作所 正极活性物质、正极、电池、电池包、电子设备、电动车辆、蓄电装置以及电力系统
CN111971822A (zh) * 2018-04-04 2020-11-20 斯普林鲍尔国际公司 用于锂离子电池的正极材料的生产方法
JP7198600B2 (ja) * 2018-07-04 2023-01-04 本田技研工業株式会社 正極活物質粒子
JP7041023B2 (ja) 2018-07-31 2022-03-23 トヨタ自動車株式会社 リチウムイオン電池用正極活物質及びリチウムイオン電池
JP7168373B2 (ja) * 2018-08-03 2022-11-09 トヨタ自動車株式会社 リチウムイオン電池用正極活物質
JP7310118B2 (ja) * 2018-10-29 2023-07-19 セイコーエプソン株式会社 正極材の製造方法
CN111564612B (zh) * 2020-04-07 2022-09-06 江门市科恒实业股份有限公司 一种高导热导电性锂电正极材料及其制备方法
US20230246183A1 (en) * 2020-06-05 2023-08-03 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material, positive electrode active material layer, secondary battery, electronic device, and vehicle
US20240379941A1 (en) * 2021-07-09 2024-11-14 Semiconductor Energy Laboratory Co., Ltd. Positive electrode active material
JPWO2023037776A1 (enrdf_load_stackoverflow) * 2021-09-13 2023-03-16
JPWO2023037775A1 (enrdf_load_stackoverflow) * 2021-09-13 2023-03-16
JPWO2023248053A1 (enrdf_load_stackoverflow) * 2022-06-22 2023-12-28

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000164214A (ja) * 1998-11-25 2000-06-16 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2013101908A (ja) * 2011-11-07 2013-05-23 Samsung Sdi Co Ltd 電極活物質及びその製造方法、並びにそれを採用した電極及びリチウム電池
JP2014089869A (ja) * 2012-10-30 2014-05-15 Sanyo Electric Co Ltd 非水電解質二次電池
WO2014132550A1 (ja) * 2013-02-28 2014-09-04 三洋電機株式会社 非水電解質二次電池用正極、及びその正極を用いた非水電解質二次電池
JP2014216077A (ja) * 2013-04-23 2014-11-17 日立マクセル株式会社 非水電解質リチウムイオン二次電池用正極材料およびその正極材料を用いた非水電解質リチウムイオン二次電池

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11273678A (ja) * 1998-03-23 1999-10-08 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質およびその製造方法ならびに該正極活物質を用いた非水系電解質二次電池
JP3951715B2 (ja) * 2002-01-17 2007-08-01 松下電器産業株式会社 リチウムイオン二次電池の正極活物質およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000164214A (ja) * 1998-11-25 2000-06-16 Japan Storage Battery Co Ltd 非水電解質二次電池
JP2013101908A (ja) * 2011-11-07 2013-05-23 Samsung Sdi Co Ltd 電極活物質及びその製造方法、並びにそれを採用した電極及びリチウム電池
JP2014089869A (ja) * 2012-10-30 2014-05-15 Sanyo Electric Co Ltd 非水電解質二次電池
WO2014132550A1 (ja) * 2013-02-28 2014-09-04 三洋電機株式会社 非水電解質二次電池用正極、及びその正極を用いた非水電解質二次電池
JP2014216077A (ja) * 2013-04-23 2014-11-17 日立マクセル株式会社 非水電解質リチウムイオン二次電池用正極材料およびその正極材料を用いた非水電解質リチウムイオン二次電池

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112840487A (zh) * 2018-10-15 2021-05-25 日本化学工业株式会社 锂二次电池用正极活性物质、其制造方法和锂二次电池

Also Published As

Publication number Publication date
JP6611438B2 (ja) 2019-11-27
JP2016143539A (ja) 2016-08-08

Similar Documents

Publication Publication Date Title
JP6611438B2 (ja) 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池
JP6560917B2 (ja) 正極材料、および正極材料を用いた非水電解質二次電池
JP6888297B2 (ja) 非水系電解質二次電池用正極活物質とその製造方法
JP6120765B2 (ja) 非水電解質二次電池用正極材料およびその製造方法、非水電解質二次電池
JP6089433B2 (ja) Ｌｉ−Ｎｉ複合酸化物粒子粉末及びその製造方法、並びに非水電解質二次電池
JP4318313B2 (ja) リチウム二次電池用の正極活物質粉末
CN102037589B (zh) 锂电池用橄榄石型正极活性材料前体、锂电池用橄榄石型正极活性材料、制备方法和锂电池
JP6533734B2 (ja) リチウムイオン電池用正極活物質、リチウムイオン電池用正極及びリチウムイオン電池
JP5987401B2 (ja) 非水系電解質二次電池用正極活物質とその製造方法および二次電池
JP5282170B1 (ja) 非水電解質二次電池
CN104282879A (zh) 正极活性物质、其制备方法、及正极和可再充电锂电池
JP6274536B2 (ja) リチウム二次電池用混合活物質の製造方法、リチウム二次電池用電極の製造方法及びリチウム二次電池の製造方法
TW201424100A (zh) Ｌｉ－Ｎｉ複合氧化物粒子粉末以及非水電解質蓄電池
WO2021251416A1 (ja) リチウムイオン二次電池用正極活物質、その製造方法、およびリチウムイオン二次電池
JP2017139168A (ja) 非水電解質二次電池用正極
JP6068247B2 (ja) 非水電解質リチウムイオン二次電池用正極材料およびその正極材料を用いた非水電解質リチウムイオン二次電池
JP2015166291A (ja) リチウム複合酸化物
JP2015041600A (ja) リチウムイオン二次電池用のリチウム含有複合酸化物の製造方法
JP7274125B2 (ja) 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池
CN112993237A (zh) 用于锂二次电池的负极材料及其制造方法
JP7177395B2 (ja) 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池
JP2022504835A (ja) リチウム遷移金属複合酸化物およびその製造方法
JP2021009778A (ja) リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池
JP2021131933A (ja) 非水電解質二次電池用正極材料及びその製造方法、並びに非水電解質二次電池
JP7454642B1 (ja) リチウム金属複合酸化物、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15880050

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15880050

Country of ref document: EP

Kind code of ref document: A1