WO2006009177A1 - リチウム二次電池用正極活物質及びその製造方法 - Google Patents
リチウム二次電池用正極活物質及びその製造方法 Download PDFInfo
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- WO2006009177A1 WO2006009177A1 PCT/JP2005/013325 JP2005013325W WO2006009177A1 WO 2006009177 A1 WO2006009177 A1 WO 2006009177A1 JP 2005013325 W JP2005013325 W JP 2005013325W WO 2006009177 A1 WO2006009177 A1 WO 2006009177A1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a positive electrode active material for a lithium ion secondary battery and a method for producing the same, particularly having high safety, high discharge voltage, high capacity, and high cycle characteristics.
- LiCoO is often used in terms of safety and capacity. This material is for charging
- Patent Document 1 LiCoO to aluminum
- Patent Document 5 Although there was an attempt to do so, the safety was unsatisfactory (Patent Document 5).
- Patent Document 1 Patent 3797693
- Patent Document 2 WO2002 / 54512
- Patent Document 3 WO2003 / 38931
- Patent Document 4 Japanese Patent Application Laid-Open No. 2004-47437
- Patent Document 5 JP 2002-352802
- An object of the present invention is to provide a positive electrode active material for a lithium ion secondary battery having high safety, high discharge voltage, high capacity, and excellent cycle durability, and a method for producing the same. Means for solving the problem
- a positive electrode active material for lithium secondary batteries made of granular lithium cobaltate-based composite oxides containing fluorine is a high-performance battery with safety, charge / discharge cycle characteristics, high discharge voltage, and high fillability. It was found to have positive electrode characteristics.
- the present inventor makes the effects of these contained elements effectively by allowing the above-mentioned Ti, Nb, and / or Ta to be present on the surface of the particulate lithium cobalt oxide-based composite oxide. Therefore, it has been found that it is more preferable.
- the positive electrode material for a lithium secondary battery of the present invention has the following gist.
- the positive electrode active material for lithium secondary batteries according to (1) above which is 25.
- Particulate form represented by positive electrode active material for lithium ion secondary battery A method for producing a positive electrode active material for a lithium ion secondary battery comprising a lithium cobalt-based composite oxide, comprising: at least one of cobalt cobalt hydroxide, cobalt tetroxide, or cobalt hydroxide; A lithium secondary battery characterized by firing a mixture of a lithium raw material, an aluminum raw material, a magnesium raw material, an element A raw material, and, if necessary, a fluorine raw material in an oxygen-containing atmosphere at 800 to 1050 ° C. For producing a positive electrode active material for use.
- the mechanism of why the positive electrode active material for a lithium secondary battery of the present invention exhibits high safety and good cycle characteristics and a high discharge voltage is not always clear, but as follows Presumed.
- the element A, aluminum, and magnesium are added simultaneously, and all or a part thereof is in solid solution.
- the oxygen element in the crystal lattice becomes stable, and as a result, the safety is improved.
- the uneven distribution of the element A on the surface of the positive electrode particles results in a thin coating film derived from the electrolyte formed on the positive electrode. This also results in improved discharge cycle durability.
- the lithium cobaltate-based composite oxide constituting the positive electrode active material for a lithium ion secondary battery of the present invention is represented by the above general formula (1): LiCoAlMgAOF.
- A, a, b, c, d, and e are as described above. If the above-mentioned ranges of a and b are deviated, the discharge capacity is lowered or the charge / discharge cycle durability is lowered. If c, d, and e are below their lower limits, the effect of improving safety, discharge voltage, and charge / discharge cycle endurance is reduced, which is not preferable. If c, d, e, and g exceed their upper limits, the discharge capacity decreases, which is preferable.
- A is preferred for titanium, and particularly preferred for c, d, e and g. 0.0003 ⁇ c ⁇ 0.01, 0.0003 ⁇ d ⁇ 0.01, 0.002 ⁇ e ⁇ 0.007 0 ⁇ g ⁇ 0.01, 0. 0005 ⁇ c + d + e 02.
- the atomic ratio c of A1 and the atomic ratio d of Mg are 0.5 ⁇ cZd ⁇ 2, and the strength is 0.002 ⁇ c + d ⁇ 0.025. I like it.
- the positive electrode active material is preferable because the discharge capacity is hardly lowered while ensuring safety.
- the atomic ratio of element A and Mg is such that the atomic ratio of 0.01 ⁇ e / d ⁇ l and 0.002 ⁇ e + d ⁇ 0.02 I like it.
- eZd is 0.01 or less, the effect of improving the discharge voltage is reduced, and the effect of improving the durability of the charge / discharge cycle is lowered.
- the force is 0.02 ⁇ e / d ⁇ 0.07 and the force is 0.005 ⁇ e + d ⁇ 0.015.
- the lithium cobalt composite oxide represented by the general formula (1) at least a part of the elements represented by Al, Mg, and A replaces the cobalt atom of the lithium cobalt composite oxide particles. It is preferable that it is a solid solution. It has also been found that safety is improved if the amount of A1 contained is small as a single oxide. And Chikarabe, in the present invention, A1 contained as a single oxide, less than 20 mole 0/0 of the total A1 contained in the lithium cobalt composite oxide, preferably be 10 mol 0/0 or less preferable.
- the positive electrode active material for a lithium secondary battery comprising the lithium cobalt-based composite oxide of the present invention is preferably in the form of spherical particles, and the average particle diameter (D50 determined by a laser scattering particle size distribution meter, The same shall apply hereinafter) but preferably 2-20 xm, in particular 3-15 ⁇ m Is preferred. If the average particle size is less than 2 zm, it is difficult to form a dense electrode layer. Conversely, if it exceeds 20 xm, it is difficult to form a smooth electrode layer surface, which is preferable. Absent.
- the positive electrode active material is preferably a particle formed by agglomerating 10 or more primary particles of fine particles to form secondary particles, thereby improving the packing density of the active material in the electrode layer. It is possible to improve the large current charge / discharge characteristics.
- the elements A and Z or F are present substantially uniformly on the particle surface.
- “uniformly present” means not only when the above-mentioned elements are substantially uniformly present near the particle surface, but also when the abundance of the above-mentioned elements between the particles is substantially equal. In particular, it is preferable that either one or both of them is satisfied and that both are satisfied. That is, it is particularly preferable that the amount of each element present between the particles is substantially equal and that each element is uniformly present on the surface of one particle.
- the element A and / or F is present on the particle surface, in other words, the element A or F is substantially present inside the particle. It ’s a good thing. By doing so, the effect can be expressed by adding a small amount of the elements A and F.
- the elements A and F When contained in the element Al, Mg, element A or fluorine atom inside the particle, a large amount is required to develop high safety, high discharge voltage, high capacity, and high cycle characteristics. If added in a large amount, the initial capacity is lowered and the large current discharge characteristics are deteriorated. Therefore, it is desirable that it be present only on the surface with a small amount of additive.
- the elements A and F preferably have a particle surface force of preferably within 1 OO nm, particularly preferably within 30 nm.
- a portion of Al and element A present in the positive electrode active material is preferably a solid solution in which cobalt atoms in the particles are substituted. It is preferable that a part of Mg present in the positive electrode active material is a solid solution in which lithium atoms inside the particles are substituted. In such a case, cobalt and oxygen atoms on the surface of the positive electrode active material particles are not exposed, and therefore, the effect of the additive element is more preferable.
- the addition of fluorine atoms is preferable because it has the effect of improving battery safety and cycle characteristics.
- the atomic ratio of the fluorine atom to the cobalt atom is preferably 0.0001 to 0.02 in order to improve the safety of the cyclone, particularly ⁇ or 0.005 to. 0.008 force S is preferred. If the atomic ratio of fluorine atoms is larger than this ratio, the discharge capacity will decrease significantly.
- the particulate positive electrode active material of the present invention preferably has a press density of 3.0 to 3.4 gZcm 3 .
- the press density is smaller than 3. OgZcm 3 , the initial volume capacity density of the positive electrode when the positive electrode sheet is formed using the particulate positive electrode active material is low, and conversely, it is larger than 3.4 g / cm 3 .
- the initial weight capacity density of the positive electrode is lowered, and the discharge and discharge characteristics of the positive electrode are lowered.
- the press density of the particulate positive electrode active material is preferably 3.15 to 3.3 g / cm 3 .
- the press density means a value obtained from the volume and powder weight when the powder is pressed at a pressure of 0.32 t / cm 2 .
- the specific surface area of the particulate positive electrode active material of the present invention is preferably 0.2 to lm 2 / g.
- the specific surface area is smaller than 0.2 m 2 / g, the discharge capacity per initial unit weight decreases, and conversely when the specific surface area exceeds lm 2 / g, the discharge capacity per initial unit volume decreases.
- a positive electrode active material excellent in the purpose of the present invention cannot be obtained.
- the specific surface area is preferably 0.3 to 0.7 m 2 / g.
- the method for producing the particulate positive electrode active material of the present invention is not necessarily limited, and can be produced by a known method.
- Al, Mg, and elements A and F are exemplified as a preferable method in which a solid powder containing each element is dry-mixed with a cobalt raw material powder and a lithium raw material powder and then fired. .
- various methods can be applied as methods for adding these Al, Mg, elements A and F to the cobalt raw material powder and the lithium raw material powder. That is, the solid, misaligned or all solid compounds containing Al, Mg, and elements A and F are dissolved or dispersed in an aqueous solution, an organic solvent, etc., and an organic acid or hydroxyl group-containing organic substance capable of forming a complex is added. Then, a uniform solution or a colloidal solution is obtained, and the cobalt raw material powder is impregnated and dried, so that the cobalt raw material uniformly supports Al, Mg, elements A and F, and then the lithium raw material powder. Are mixed and fired.
- the above homogeneous solution or colloidal solution, cobalt raw material powder and lithium raw material powder are mixed and dried and then fired. Therefore, high battery performance can be obtained.
- the distribution of elements in the particles is different compared to the case of adding elements by the solid phase method, it may be necessary to change the amount of elements to be added.
- Examples of the raw material used in the production of the present invention include cobalt hydroxide, cobalt tetroxide, cobalt oxyhydroxide, and cobalt oxyhydroxide, which exhibits high battery performance. Preference is given to tribasic cobalt oxide or cobalt hydroxide. In particular, since the press density can be increased, it is preferable to use a substantially spherical cobalt oxyhydroxide having many primary particles agglomerated to form secondary particles as a cobalt raw material.
- cobalt raw material a cobalt raw material that is composed of particles in which 10 or more primary particles are aggregated to form secondary particles and contains at least either oxycobalt hydroxide or cobalt hydroxide is high. This is preferable because battery performance is obtained.
- the raw materials for Al, Mg and element A include oxides, hydroxides, chlorides, nitrates, organic acid salts, oxyhydroxides, fluorides, and water that is easy to achieve high battery performance. Oxides and fluorides are preferred.
- As the lithium raw material lithium carbonate and lithium hydroxide are preferable.
- As the fluorine raw material lithium fluoride, aluminum fluoride or magnesium fluoride is preferable.
- a mixture of these raw materials preferably (1) A1, element A and Mg-containing oxide, or Al, element A and Mg-containing hydroxide, (2) cobalt hydroxide, oxycobalt hydroxide Or a mixture of (1) to (4) of cobalt oxide, (3) lithium carbonate, and optionally (4) lithium fluoride, in an oxygen-containing atmosphere from 600 to 1050 ° C, preferably from 850 to It is produced by calcination at 1000 ° C., preferably for 4 to 48 hours, particularly for 8 to 20 hours, and converted into a composite oxide.
- fluoride containing Al, element A or Mg may be used instead of element A and lithium fluoride.
- an oxygen-containing atmosphere containing an oxygen concentration of preferably 10% by volume or more, particularly 40% by volume or more.
- a composite oxide can satisfy the above-described present invention by changing the kind of each raw material, the mixed composition, and the firing conditions.
- preliminary firing can be performed in the above firing.
- Pre-baking Is carried out in an oxidizing atmosphere, preferably at 450 to 550 ° C., preferably for 4 to 20 hours.
- the production of the positive electrode active material of the present invention is not necessarily limited to the above-described method.
- the positive electrode active material is synthesized using a metal fluoride, an oxide and Z or a hydroxide as a raw material.
- fluorinating agents such as fluorine gas, NF, HF
- the method for obtaining a positive electrode for a lithium secondary battery from the particulate positive electrode active material of the present invention can be carried out according to a conventional method.
- a positive electrode mixture is formed by mixing a carbon-based conductive material such as acetylene black, graphite, and ketjen black with a binder in the positive electrode active material powder of the present invention.
- a binder polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethyl cellulose, acrylic resin, or the like is used.
- a slurry in which the above-mentioned positive electrode mixture is dispersed in a dispersion medium such as N-methylpyrrolidone is coated on a positive electrode current collector such as aluminum foil, dried and press-rolled to form a positive electrode active material layer. Formed on the current collector.
- a carbonate of the electrolyte solution is preferable.
- the carbonate ester can be either cyclic or chain.
- the cyclic carbonate include propylene carbonate and ethylene carbonate (EC).
- the chain carbonic acid ester include dimethyl carbonate, jetyl carbonate (DEC), ethinoremethinorecarbonate, methinorepropinolecarbonate, methinoreisopropyl pyrcarbonate and the like.
- the carbonate ester may be used alone or in combination of two or more. Further, it may be used by mixing with other solvents. Depending on the material of the negative electrode active material, the combined use of chain carbonate and cyclic carbonate may improve discharge characteristics, cycle durability, and charge / discharge efficiency.
- a gel polymer electrolyte may be obtained by covering the following solutes.
- Solutes in the electrolyte solution include ClO-, CFSO_, BF-, PF-, AsF-, SbF
- Lithium salt with anion as one or more
- an electrolyte composed of a lithium salt is preferably added to the solvent or the solvent-containing polymer at a concentration of 0.2 to 2 OmolZL. Outside this range, the ionic conductivity decreases and the electrical conductivity of the electrolyte decreases. More preferably, 0.5 to: 1.5 mol / L is selected.
- a porous polyethylene film or a porous polypropylene film is used.
- the negative electrode active material of a lithium battery using the positive electrode active material of the present invention for the positive electrode is a material capable of occluding and releasing lithium ions.
- the material for forming the negative electrode active material is not particularly limited, but for example, lithium metal, lithium alloy, carbon material, periodic table 14, oxide mainly composed of group 15 metal, carbon compound, carbide compound, oxide Examples include silicon compounds, titanium sulfide, and boron carbide compounds.
- the carbon material those obtained by pyrolyzing organic substances under various pyrolysis conditions, artificial graphite, natural graphite, soil graphite, expanded graphite, flake graphite, and the like can be used.
- the oxide a compound mainly composed of tin oxide can be used.
- the negative electrode current collector a copper foil, a nickel metal foil or the like is used.
- the shape of the lithium secondary battery using the positive electrode active material in the present invention is not particularly limited.
- a sheet shape (so-called film shape), a folded shape, a wound-type bottomed cylindrical shape, a button shape, and the like are selected depending on the application.
- the high-sensitivity X-ray diffraction spectrum means a diffraction spectrum obtained at an acceleration voltage of the X-ray tube of 50 KV—acceleration current of 250 mA.
- the normal X-ray diffraction spectrum is 40KV—acceleration current around 40mA.
- the average particle size D50 is 13.2 ⁇ m, where 50 or more primary particles aggregate to form secondary particles.
- Cobalt hydroxide powder, lithium carbonate powder with an average particle size of 15 ⁇ m, aluminum hydroxide powder with a particle size of 1.5 ⁇ m, magnesium hydroxide powder with an average particle size of 3.7 xm, and an average particle size of 0 A predetermined amount of 6 ⁇ m titanium oxide powder was mixed. After these four types of powders were dry-mixed, they were baked in the atmosphere at 400 ° C for 3 hours and then at 950 ° C for 10 hours. As a result of wet-dissolving the fired powder and measuring the contents of cobalt, aluminum, magnesium, titanium and lithium by ICP and atomic absorption spectrometry, the composition of the powder was LiCo Al Mg Ti
- the specific surface area determined by the nitrogen adsorption method of the powder was 0.37 m 2 / g, and the average particle diameter D50 was 13.8 / im.
- a strong signal of A12P attributed to aluminum and a strong signal of Ti2P attributed to titanium were detected.
- the press density of this positive electrode powder was 3.25 g / cm.
- the trifluoroethylene powder was mixed at a weight ratio of 80/16/16, and kneaded and dried while adding toluene to prepare a positive electrode plate having a thickness of 150 ⁇ .
- An aluminum foil having a thickness of 20 ⁇ is used as a positive electrode current collector, porous polypropylene having a thickness of 25 ⁇ m is used as a separator, and a metal lithium foil having a thickness of 500 ⁇ m is used as a negative electrode. Les, negative Nickel foil 20 ⁇ m is used for the current collector, and lMLiPF / EC + DEC (1: 1) is used for the electrolyte.
- positive electrode active material lg was charged to 4.3 V with a load current of 75 mA at 25 ° C, and positive electrode active material lg was discharged to 2.75 V with a load current of 75 mA and initially discharged. The capacity was determined. Furthermore, the charge / discharge cycle test was conducted 14 times.
- Another similar battery was produced. For this battery, charge it at 4.3V for 10 hours, disassemble it in an argon glove box, take out the charged positive electrode sheet, wash the positive electrode sheet, punch it out to 3mm in diameter, and put it into an aluminum capsule with EC It was sealed and heated at a rate of 5 ° C / min with a scanning differential calorimeter, and the heat generation start temperature was measured. As a result, the heat generation start temperature of the 4.3V charged product was 167 ° C.
- a positive electrode active material was synthesized in the same manner as in Example 1 except that niobium oxide was used instead of using titanium oxide, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition was LiCo Al Mg Nb O.
- the specific surface area obtained by the nitrogen adsorption method of the powder after firing was 0.32 m 2 / g, and the average particle diameter D50 obtained by a laser scattering particle size distribution analyzer was 13.5 ⁇ m. It was. Aluminum and niobium were present on the surface.
- the initial discharge capacity at 25 ° C, 2.75 to 4.3 V, discharge rate 0.5 C was 162.0 mAh / g, and the average voltage was 3.974 V.
- the capacity retention rate after 14 charge / discharge cycles was 99.2%.
- the exotherm starting temperature was 165 ° C.
- the press density of this positive electrode powder was 3.26 gm 3 .
- a positive electrode active material was synthesized in the same manner as in Example 1 except that tantalum oxide was used instead of titanium oxide, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition was LiCo Al Mg Ta O.
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.30 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 13.3 ⁇ m. It was. Aluminum and tantalum were present on the surface.
- the initial discharge capacity at 25 ° C, 2.75 ⁇ 4.3V, discharge rate 0.5C was 161.8mAh / g, and the average voltage was 3.974V.
- the capacity retention rate after 14 charge / discharge cycles was 99.2%.
- the heat generation starting temperature was 165 ° C.
- the press density of this positive electrode powder was 3.24 gm 3 .
- Example 2 50 particles of primary particles aggregated to form secondary particles Average particle size D50 of 10.7 ⁇ m cobalt hydroxide hydroxide powder, lithium carbonate powder, aluminum hydroxide powder, magnesium hydroxide powder
- a positive electrode active material was synthesized in the same manner as in Example 1 except that a predetermined amount of titanium oxide powder and lithium fluoride powder were mixed, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition is LiCo Al Mg Ti OF.
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.34 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 12. .
- Aluminum, titanium and fluorine were present on the surface.
- the obtained positive electrode active material powder was aggregated with 30 or more primary particles to form secondary particles.
- the press density of the positive electrode powder was m 3 N 3. 23 g.
- the initial discharge capacity at 25 ° C, 2.75 to 4.3 V, discharge rate of 0.5 C was 161.5 mAh / g, and the average voltage was 3.976 V.
- the capacity retention rate after 14 charge / discharge cycles was 99.3%.
- the heat generation starting temperature of the 4.3V charged product was 170 ° C.
- a positive electrode active material was synthesized in the same manner as in Example 1, except that aluminum hydroxide powder, magnesium hydroxide powder, and titanium oxide powder were not used. Composition analysis, physical property measurement, and battery performance test were performed. Went. As a result, the composition was LiCoO.
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.32 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 13.4 / im. Met.
- the press density of the positive electrode powder was m 3 N 3. 25 g.
- the initial discharge capacity at 25 ° C, 2.75 to 4.3 V, discharge rate 0.5 C was 161.9 mAh / g, and the average voltage was 3.96 IV.
- the capacity retention rate after 14 charge / discharge cycles was 97.8%.
- the heat generation start temperature of the 4.3V charged product was 160 ° C.
- a positive electrode active material was synthesized in the same manner as in Example 1 except that titanium oxide was not used, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition is LiCo A1
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.34 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 13. .
- Aluminum was present on the surface. Further, the press density of the positive electrode powder had a m 3 N 3. 25 g
- the initial discharge capacity at 25 ° C, 2.75 to 4.3 V, discharge rate 0.5 C was 161. OmAh / g, and the average voltage was 3.964 V.
- the capacity retention rate after 14 charge / discharge cycles was 98.7%.
- the heat generation starting temperature of the 4.3V charged product was 167 ° C.
- a positive electrode active material was synthesized in the same manner as in Example 1 except that magnesium hydroxide was not used, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition was Li Co Al Ti O.
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.30 m 2 / g, and the average particle diameter D50 determined by a laser-scattering particle size distribution analyzer was 13. . Aluminum and titanium were present on the surface.
- the press density of this positive electrode powder was 3.24 gm 3 .
- a positive electrode active material was synthesized in the same manner as in Example 1 except that the addition amounts of aluminum hydroxide, magnesium hydroxide, and titanium oxide were changed, and composition analysis, physical property measurement, and battery performance test were performed. As a result, the composition was LiCo Al Mg Ti O.
- the specific surface area determined by the nitrogen adsorption method of the powder after firing was 0.33 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 13.5 ⁇ m. It was. Aluminum and titanium were present on the surface.
- the initial discharge capacity at 25 ° C, 2.75 to 4.3 V, discharge rate 0.5 C was 160. OmAh / g, and the average voltage was 3.976 V.
- the capacity retention rate after 14 charge / discharge cycles was 99.5%.
- the heat generation start temperature was 170 ° C.
- the press density of this positive electrode powder was 3.20 gm 3 .
- Magnesium carbonate powder 1.97 g, citrate 2.88 g and water 133.20 g are added, and ammonia is added 1.50 g to obtain a salt of carboxylic acid power in which magnesium at pH 9.5 is uniformly dissolved.
- An aqueous solution was obtained.
- the above aqueous solution was made into a slurry free of calories from 193.4 g of hydroxyaluminate having an average particle diameter D50 of 13.5 x m, D10 of 5.5 x m, and D90 force of 8.1 ⁇ m.
- the solid content concentration in the slurry was 76% by weight.
- This slurry was dehydrated in a dryer at 120 ° C. for 2 hours to obtain a magnesium-added cobalt hydroxide powder.
- This slurry was dehydrated in a dryer at 120 ° C for 2 hours to obtain magnesium-aluminum-added cobalt oxide powder.
- LiCo Al Mg Ti O was obtained by mixing 0.08 g of titanium oxide and 74.5 g of lithium carbonate with this magnesium-added cobalt hydroxide powder and firing in air at 950 ° C for 12 hours. .
- the specific surface area of the powder after calcination determined by the nitrogen adsorption method was 0.33 m 2 / g, and the average particle size D50 determined by a laser scattering particle size distribution analyzer was 13.7 ⁇ m. It was. Magnesium and aluminum were uniformly present in the particles. Titanium was present on the surface. twenty five.
- the initial discharge capacity at C, 2.75 to 4.3 V, discharge rate 0.5 C was 162. OmAh Zg, and the average voltage was 3.977 V.
- the capacity retention rate after 14 charge / discharge cycles was 99.6%.
- the heat generation starting temperature was 169 ° C.
- the press density of the positive electrode powder was m 3 N 3. 23 g.
- the lithium ion secondary battery is useful for a lithium ion secondary battery and has high discharge voltage, high capacity, high cycle durability, and high safety.
- a positive electrode material is provided.
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
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JP2006529249A JP5080808B2 (ja) | 2004-07-20 | 2005-07-20 | リチウム二次電池用正極活物質及びその製造方法 |
US11/625,060 US20070117014A1 (en) | 2004-07-20 | 2007-01-19 | Positive electrode active material for lithium secondary battery and method for producing same |
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- 2005-07-20 JP JP2006529249A patent/JP5080808B2/ja not_active Expired - Fee Related
- 2005-07-20 CN CNA2005800224571A patent/CN1981396A/zh active Pending
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JP2009212021A (ja) * | 2008-03-06 | 2009-09-17 | Hitachi Maxell Ltd | 電気化学素子用電極、非水二次電池および電池システム |
JP2010086922A (ja) * | 2008-10-02 | 2010-04-15 | Toda Kogyo Corp | リチウム複合化合物粒子粉末及びその製造方法、非水電解質二次電池 |
JP2013232438A (ja) * | 2013-08-05 | 2013-11-14 | Toda Kogyo Corp | リチウム複合化合物粒子粉末及びその製造方法、非水電解質二次電池 |
JP2017021942A (ja) * | 2015-07-09 | 2017-01-26 | 日立マクセル株式会社 | 正極材料、および正極材料を用いた非水電解質二次電池 |
US11799080B2 (en) | 2017-05-19 | 2023-10-24 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
JP2020024942A (ja) * | 2017-06-26 | 2020-02-13 | 株式会社半導体エネルギー研究所 | リチウムイオン二次電池の正極活物質の作製方法 |
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Also Published As
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KR100995255B1 (ko) | 2010-11-19 |
KR20070033337A (ko) | 2007-03-26 |
US20070117014A1 (en) | 2007-05-24 |
JP5080808B2 (ja) | 2012-11-21 |
CN1981396A (zh) | 2007-06-13 |
JPWO2006009177A1 (ja) | 2008-05-01 |
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