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WO2008013208A1 - Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et procédé de production de celui-ci - Google Patents

Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et procédé de production de celui-ci Download PDF

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Publication number
WO2008013208A1
WO2008013208A1 PCT/JP2007/064606 JP2007064606W WO2008013208A1 WO 2008013208 A1 WO2008013208 A1 WO 2008013208A1 JP 2007064606 W JP2007064606 W JP 2007064606W WO 2008013208 A1 WO2008013208 A1 WO 2008013208A1
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Prior art keywords
lithium
positive electrode
composite oxide
active material
titanium
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English (en)
Japanese (ja)
Inventor
Yukimitsu Wakasugi
Nozomi Honda
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AGC Seimi Chemical Ltd
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AGC Seimi Chemical Ltd
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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 used for a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.
  • a manufacturing method thereof, and a lithium secondary battery including the positive electrode active material are provided.
  • non-aqueous electrolyte secondary batteries such as lithium secondary batteries having a small size, light weight, and high energy density have been developed with the rapid development of information-related equipment and communication equipment such as personal computers and mobile phones.
  • the demand for is increasing.
  • the positive electrode active materials for non-aqueous electrolyte secondary batteries include LiCoO, LiNiO, LiNi CoO, LiNi Co Mn O, LiMn O, etc.
  • lithium cobalt composite oxide (LiCoO) is used as the positive electrode active material.
  • Lithium secondary batteries using carbon such as rum alloy, graphite, and carbon fiber as a negative electrode are particularly widely used as batteries having a high energy density because they can provide a high voltage of 4V.
  • lithium nickel cobalt (Li Ni—Co) composite oxide lithium nickel cobalt manganese (Li Ni—Co—Mn) composite oxide and! /
  • a positive electrode active material are also attracting attention.
  • These positive electrode active materials have characteristics that battery characteristics such as charge / discharge cycle characteristics, rate characteristics, and safety can be adjusted by adjusting the amount of nickel, cobalt, or manganese added.
  • the discharge capacity, charge / discharge cycle characteristics, rate characteristics, and stability during charging in this specification, safety and I was not able to satisfy all of these characteristics.
  • lithium and titanium oxide coated with titanium oxide are obtained by adding water and ammonium oxalate to a lithium-containing composite oxide synthesized beforehand, followed by stirring, spray drying, crushing, and heat treatment.
  • a composite oxide containing the same has been proposed (see Patent Document 3).
  • lithium-containing composite oxide obtained by heat treatment at 500 ° C
  • lithium nickel composite in acetone solution in which titanium oxide sol is dispersed There has been proposed a surface-modified lithium nickel composite oxide (see Patent Document 5) obtained by adding an oxide, stirring, evaporating and drying, followed by heat treatment at 500 ° C.
  • a lithium-containing composite oxide is dispersed in an ethanol solution of Ti (OC H) and dried.
  • Patent Document 1 JP-A-2005-123111
  • Patent Document 2 JP-A-4 329267
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-6676
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2002-151078
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004-253305
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2005-310744
  • Patent Document 7 JP 2002-63901 A
  • the lithium-containing composite oxide powder obtained in the above-mentioned patent documents;! To 7 has the above characteristics when used as a positive electrode active material of a non-aqueous electrolyte secondary battery such as a lithium secondary battery.
  • the discharge capacity and charge / discharge cycle characteristics are inadequate, and further improvements are required rather than those that can sufficiently satisfy the characteristics such as safety at the same time.
  • the charging voltage is generally 4.3. Although it is V, it is desired to increase the charging voltage, increase the amount of the positive electrode active material that can be used, and further improve the discharge capacity.
  • the utilization rate of the positive electrode active material is 50 to 60%.
  • the utilization rate can be improved to about 70% and the discharge capacity can be increased. It can be improved dramatically.
  • the lithium-containing composite oxides obtained in the above-mentioned patent documents;! To 7 do not have sufficient charge / discharge cycle characteristics at a charge voltage of 4.3 V, and are charged at a high operating voltage of a charge voltage of 4.5 V. The discharge cycle characteristics are further deteriorated.
  • An object of the present invention is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery having a high discharge capacity even at a high operating voltage with high safety and excellent charge / discharge cycle characteristics, a method for producing the same, and
  • the present invention provides a non-aqueous electrolyte secondary battery such as a lithium secondary battery containing the positive electrode active material.
  • the inventors of the present invention have made extensive studies and found that they are lithium-containing composite oxide particles having a specific composition, and a specific surface region containing a relatively high specific concentration of titanium. It has been found that the above object can be achieved by a positive electrode active material comprising modified lithium-containing composite oxide particles. That is, it has been found that by using a positive electrode that is strong and has a high discharge capacity even at a high operating voltage with high safety, and excellent charge / discharge cycle characteristics can be achieved.
  • the mechanism of why excellent characteristics are achieved by the lithium-containing composite oxide particles is not necessarily clear, but is estimated as follows.
  • a decomposition reaction of the electrolyte occurs at the interface between the lithium-containing composite oxide particles and the electrolyte, and a gas containing carbon dioxide is generated. Occurs.
  • surface-modified lithium-containing composite oxide particles containing a relatively high concentration of titanium in the surface region are used, the active sites on the surface of the lithium-containing composite oxide particles react with titanium.
  • the decomposition reaction of the electrolytic solution is suppressed, and a high operating voltage, a high volume capacity density, and a high safety are maintained.
  • a relatively high concentration of titanium is present in the surface layer of the lithium-containing composite oxide particles, electrolysis of the active component in the lithium-containing composite oxide particles will occur.
  • the charge / discharge cycle characteristics are remarkably improved not only when the operating voltage is 4.3V, but also at a particularly high operating voltage of 4.5V.
  • the conventional lithium-containing composite oxide particles described above contain titanium.
  • the content of titanium is large, and the titanium content in the surface layer is not particularly large.
  • the lithium-containing composite oxide described in Patent Document 1 described above is fired at a high temperature of 995 ° C. after the addition of the titanium powder, so that the solid solution diffusion of the additive element proceeds and the particles are relatively dispersed. From the inner particle surface 50 ⁇ ; OOnm range contains more than 20% titanium. That is, the atomic ratio of titanium in the surface layer within 5 nm of the lithium-containing composite oxide described in Patent Document 1 is at most about 0.5 with respect to the element N.
  • the element N represents cobalt, manganese, and nickel contained in the lithium-containing composite oxide particles, and represents cobalt in the examples of Patent Document 1.
  • the lithium-containing composite oxide described in Patent Document 2 is subjected to heat treatment at a high temperature of 900 ° C after chemically modifying the particle surface with a titanium coupling agent, and the surface layer of the lithium-containing composite oxide
  • the atomic ratio of titanium within 5 nm is at most about 0.08 with respect to element N as described in the literature.
  • the atomic ratio of titanium in the surface layer within 5 nm is at most about 0.16 with respect to the element N as described in the document.
  • Patent Document 4 a titanium hydroxide colloid aqueous solution is used, and in Patent Document 5, a titanium compound is modified on the surface of a particle using an acetone solution of a titanium oxide sol, followed by heat treatment at 500 ° C.
  • a sol-gel method When such a sol-gel method is used, the atomic ratio of titanium in the surface layer of 5 nm or less of the lithium-containing composite oxide particles, which is extremely thin on the particle surface and difficult to contain titanium at a specific ratio, is relative to the element N.
  • Patent Document 6 and Patent Document 7 using a solution of Ti (OEt) in ethanol, the surface of the particle is at most 0.5.
  • the surface layer of the surface-modified lithium-containing composite oxide obtained after heat treatment The atomic ratio of titanium inside is about 0.5 at most.
  • the present invention is based on the above novel findings and has the following gist.
  • Lithium-containing composite oxide particles, titanium is contained in the surface layer, and a positive electrode for a non-aqueous electrolyte secondary battery comprising surface-modified lithium-containing composite oxide particles having an atomic ratio of 0.6 or more with respect to titanium content force S and element N within 5 nm of the surface layer Active material.
  • the lithium-containing composite oxide particles are at least one particle selected from the group consisting of lithium cobaltate, lithium nickel oxide, nickel cobalt lithium aluminate and nickel cobalt lithium manganate, and The non-aqueous solution according to (1), wherein titanium contained in the entire surface-modified lithium-containing composite oxide particle has an atomic ratio of 0.0005 to 0.10 with respect to the total of the elements N and M.
  • Positive electrode active material for electrolyte secondary battery is at least one particle selected from the group consisting of lithium cobaltate, lithium nickel oxide, nickel cobalt lithium aluminate and nickel cobalt lithium manganate.
  • a lithium secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte, wherein the positive electrode active material according to any one of (1) to (5) is used for the positive electrode.
  • Lithium-containing composite oxide particles represented by 3) have a pH of 1 ⁇ including titanium complex; Step 1 of impregnating 12 aqueous solutions, mixing and drying to obtain titanium complex-impregnated particles, and Step 1 And a step 2 of heat treating the titanium complex-impregnated particles in an oxygen-containing atmosphere.
  • a non-aqueous electrolyte secondary battery comprising surface-modified lithium-containing composite oxide particles having high operating voltage, high discharge capacity, and excellent charge / discharge cycle characteristics without deteriorating high safety.
  • a positive electrode active material a method for producing the positive electrode active material, and a nonaqueous electrolyte secondary battery using the positive electrode active material.
  • FIG. 1 Infrared absorption (IR) vector (A) of the surface-modified lithium-containing composite oxide obtained in Example 2 (Example) and the lithium-containing composite obtained in Example 4 (Comparative Example) An infrared absorption (IR) spectrum (B) of the oxide is shown.
  • IR infrared absorption
  • FIG. 2 The measurement results of thermogravimetric-differential heat-differential weight (TG-DTA-DTG) separation of dried titanium lactate are shown.
  • the surface-modified lithium-containing composite oxide particles according to the present invention can be obtained by modifying the surface of lithium-containing composite oxide particles as a base material with a titanium compound.
  • Lithium-containing composite oxide particles used as a base material have the general formula Li N M O (where N is from Co, Mn and Ni).
  • At least one element selected from the group consisting of M, and M is an element selected from transition metals other than the element N, alkali earth metals, and aluminum. 0. 9 ⁇ 1.1, 0 ⁇ 9 ⁇ ⁇ 1.1, 0 ⁇ y ⁇ 0.3.
  • the element N is as described above.
  • cobalt alone, nickel alone, a combination of nickel cobalt, a combination of nickel mono-aluminum, a combination of nickel cobalt manganese From the viewpoint of further practicality, it is more preferable to use cobalt alone or a combination of nickel cobalt manganese.
  • a part of oxygen for example, 0.;! To 5 mol% may be substituted with fluorine atoms to improve battery characteristics.
  • ⁇ ⁇ ⁇ 1.1 preferably (or 0.9 95 ⁇ ⁇ ⁇ 1.05; 0. 9 ⁇ ⁇ ⁇ 1.1, preferably 0. 95 ⁇ 1.05
  • the battery characteristics can be further improved.
  • y is preferably in the range of 0 ⁇ y ⁇ 0.1 1. If an element such as titanium is excessively present inside the lithium-containing composite oxide particles, the discharge capacity may be reduced.
  • divalent to tetravalent elements such as Al, Mg, Zr, Ti, Mo, and Ca are preferably selected, and element M is particularly suitable for capacity development, safety, and charge / discharge. From the viewpoint of cycle characteristics, at least one selected from the group consisting of Ti, Zr, Mg and A1 is more preferable. Is an example of a product, LiNi Co Al O, LiNi Co Mn Al O, LiNi Co Mn
  • lithium-containing composite oxides can also be used.
  • the surface-modified lithium-containing composite oxide particles according to the present invention must have an atomic ratio of 0.6 or more with respect to the element strength N of titanium in the surface layer within 5 nm from the particle surface. is there.
  • the titanium content force S falls within the predetermined range, the above-described effects of the present invention are achieved.
  • the surface-modified lithium-containing composite oxide Titanium present near the surface of the particle is important, and the content of titanium within the surface layer of this particle within 5 nm can be easily determined by XPS analysis (X-ray photoelectron spectroscopy) as described below. .
  • atomic ratio of titanium to element N in the surface layer within 5 nm from the surface of the surface-modified lithium-containing composite oxide particle is simply referred to as “the surface ratio of the lithium-containing composite oxide particle. “Atomic ratio (Ti / N)”.
  • the atomic ratio (Ti / N) on the surface of the lithium-containing composite oxide particles is a force S that is 0.6 or more, preferably 0.7 or more, more preferably 0.8 or more, and even more preferably. Is 1.0 or higher, Particularly preferred is 1.2 or more.
  • the upper limit is not particularly limited, but the atomic ratio (Ti / N) is preferably 15 or less, more preferably 12 or less, particularly preferably 10 or less.
  • the atomic ratio (Ti / N) of the surface of the lithium-containing composite oxide particles is analyzed by XPS analysis (X-ray photoelectron spectroscopy).
  • the XPS analysis method can analyze the type of elements contained in the layer very close to the surface of the particles or the abundance of elements.
  • An example of XPS analyzer is ESCA5400 (non-monochrome type) manufactured by PHI.
  • a peak that can be detected with high sensitivity and does not overlap with the peak of other elements as much as possible is used. Is preferred.
  • titanium it is preferable to use a highly sensitive 2p peak for the calculation.
  • cobalt, manganese or nickel it is preferable to use the high sensitivity and 2p3 peak for calculation! /.
  • EPMA X-ray microanalyzer
  • EDS energy dispersive X-ray spectroscopy
  • Titanium contained in the surface-modified lithium-containing composite oxide particles according to the present invention is preferably 0.0005-0.10 in atomic ratio with respect to the total of the elements N and M in the case of the whole particles. , Especially (b. 0. 0008—0. 08
  • the titanium contained in the entire surface-modified lithium-containing composite oxide particles is preferably 0.01-0.08 in atomic ratio with respect to the total of element N and element M. Further, when the element M does not contain titanium, the titanium contained in the entire surface modified lithium-containing composite oxide particles is more preferably 0.0008 to 0.03 in atomic ratio with respect to the total of the elements N and M. .
  • the surface layer may contain elements other than titanium.
  • elements other than titanium that are preferably present in the surface layer include magnesium.
  • the surface-modified lithium-containing composite oxide particles according to the present invention may further include carbon on the surface layer. It preferably contains an elemental compound.
  • the carbon compound is preferably a partially pyrolyzed product of a carbon-containing titanium complex having a structure having at least a carbon-oxygen double bond. Among them, it is particularly preferable that the carbon-oxygen double bond is a carbonate group or a carbonyl group.
  • Specific compounds include at least one compound selected from titanium citrate, titanium tartrate, titanium oxalate, titanium malonate, titanium maleate, titanium malate, titanium phosphate, titanium lactate, and titanium dalioxylate. Partially decomposed products are preferred.
  • the partially pyrolyzed product refers to a product in which a part of the titanium complex existing on the surface of the surface-modified lithium-containing composite oxide particle is thermally decomposed, having a carbon-oxygen double bond structure.
  • FIG. 1 is a chart of infrared absorption (IR) spectrum of the lithium-containing composite oxide synthesized in Example 2 or Example 4.
  • IR infrared absorption
  • the absorption peak is an absorption peak derived from a carbon-oxygen double bond, and indicates that a carbon compound is present in the surface layer.
  • the carbon compound is a partially pyrolyzed product of the carbon-containing titanium complex used as a raw material.
  • the IR spectrum of the lithium-containing composite oxide synthesized in Example 4 shows no strong absorption peak due to the carbon-oxygen double bond.
  • Fig. 2 is a graph showing changes in weight (TG and DTG) and changes in calorific value (DTA) when heat is applied to powder obtained by drying titanium lactate (dry powder). From FIG. 2, it can be seen that when the dry powder of titanium lactate is heated to a range of 200 to 450 ° C., the weight of the dry powder decreases rapidly and is accompanied by a rapid exothermic reaction. That is, in this temperature range, it is suggested that titan lactate partially undergoes thermal decomposition, and gas such as carbon dioxide is released to promote decarboxylation. It can also be seen that the pyrolysis is almost complete above 450 ° C. This suggests that the titanium complex has been converted to titanium oxide or titanium hydroxide at this stage.
  • the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 350 ° C in Example 2 has titania having a carbon-oxygen double bond. It can be seen that a carbon compound is present in the surface layer, and that the carbon compound is a partially pyrolyzed product of the carbon-containing titanium complex used as a raw material. This is not necessarily clear about the force S that further improves the charge / discharge cycle characteristics, the reason why the charge / discharge cycle characteristics are further improved, and the mechanism.
  • the surface-modified lithium-containing composite oxide particles according to the present invention are pre-synthesized LiNi.
  • this aqueous solution may be mixed with Ti aqueous solution), mixing, drying, and heat-treating.
  • the pH of the Ti aqueous solution is preferably 1-8.
  • the titanium compound used as the raw material for the Ti aqueous solution is not particularly limited, but a titanium complex compound is preferable from the viewpoint of improving the solubility of titanium present in the aqueous solution containing titanium used for surface modification.
  • the titanium complex compound means a compound that, when dissolved in water, coordinates with titanium to form a complex.
  • the titanium compound since the above-mentioned carbon compound can remain preferably on the surface of the particle of the surface-modified lithium-containing composite oxide after the heat treatment, the titanium compound has a carbonyl group or a carbonate group, which is more preferable for the carbon-containing titanium complex.
  • the titanium compound is at least one selected from titanium citrate, titanium tartrate, titanium oxalate, titanium malonate, titanium maleate, titanium malate, titanium phosphate, titanium lactate, and titanium dalioxylate. Seeds are preferred. Of these, titanium lactate is more preferable as the titanium compound. The presence of such carbon is preferable because the charge / discharge cycle characteristics of the surface-modified lithium-containing composite oxide tend to be further improved.
  • the Ti aqueous solution contains a carboxylic acid! /, May! /.
  • a carboxylic acid is contained in the Ti aqueous solution
  • the above-mentioned carboxylic acid is a citrate, tartaric acid, oxalic acid, malonic acid, More preferred is at least one selected from the group consisting of maleic acid, phosphonic acid, dextrinic acid, lactic acid, and daroxylic acid.
  • the content of carboxylic acid in the Ti aqueous solution is preferably 0.05 to 30% by weight, particularly preferably 0.0 ;! to 20% by weight.
  • the concentration of titanium in the Ti aqueous solution is preferably higher because it is necessary to remove the aqueous medium by drying in a later step. However, if the concentration of titanium in the aqueous solution is too high, the viscosity increases, and the contact treatment with the base material or the handling of the aqueous solution tends to be complicated. For this reason, the concentration of titanium in the aqueous Ti solution is preferably 0.0;! To 20% by weight, more preferably 0.0;
  • the amount of the Ti aqueous solution is adjusted within the range of 0.;! To 80 wt% with respect to the base material used. It is even more preferable to adjust to! -75% by weight, while it is particularly preferable to adjust to 30-70% by weight.
  • the amount of the Ti aqueous solution with respect to the base material to be used is within the above range, when the positive electrode active material according to the present invention is synthesized in large quantities, the problem that the performance of the positive electrode active material varies between lots is solved, and the positive electrode active material is eliminated. This is preferable because the substance tends to be mass-produced stably.
  • the means for impregnating the lithium-containing composite oxide particles of the base material with the aqueous Ti solution is not particularly limited! Specifically, the aqueous solution of Ti is impregnated by spraying the particle powder of the base material.
  • a means for impregnating or impregnating the base material powder powder into an aqueous Ti solution contained in a container there can be used a means for impregnating or impregnating the base material powder powder into an aqueous Ti solution contained in a container.
  • the stirrer used for stirring include a twin screw kneader, an axial mixer, a paddle mixer, a turbulator, a drum mixer, a solid air, and a Laedige mixer.
  • the drying is preferably 50 to 200 ° C, particularly preferably 80 to; 140 ° C. At a temperature and preferably in the range of 0.;! To 10 hours. Since the aqueous medium remaining in the titanium complex-impregnated particles after drying is removed in a subsequent firing step, it is not necessarily completely removed at this stage, but a large amount is required to vaporize moisture in the heat treatment step. Therefore, it is preferable to remove as much energy as possible.
  • impregnation, mixing and drying may be carried out separately in order, or a Ladige mixer, etc. You can go all at the same time using
  • the titanium complex-impregnated particles are preferably heat-treated in an oxygen-containing atmosphere, preferably 200 to 450 ° C, usually 0.;! To 24 hours.
  • an oxygen-containing atmosphere preferably 200 to 450 ° C, usually 0.;!
  • the surface-modified lithium-containing composite oxide according to the present invention can be obtained.
  • a more preferable temperature range is 250 to 400 ° C.
  • Density force is preferable (2.40-3.50 g / cm 3 , especially 2.50-3.30 g / cm 3 is preferable.
  • the press density means the surface-modified lithium composite oxide particles of 0.33. It means the apparent density of the particles when pressed at a pressure of Ton'n m 2.
  • the lithium ion elution amount of the surface modified lithium-containing composite oxide of the present invention is preferred is 0.60% by mole or less Ingredients further 0-01-0 50 mol%, more preferably tool among others 0, 0;.! ⁇ 0.40 mol 0/0 are particularly preferred.
  • the lithium ion elution amount can be measured as follows. First, 10 g of the positive electrode active material powder is added to 90 g of water, and the resulting aqueous solution is stirred and dispersed for 30 minutes. It is obtained by filtering the aqueous solution with a sieve and titrating the obtained filtrate with hydrochloric acid.
  • a slurry in which the positive electrode active material powder is dispersed in a dispersion medium such as N-methylpyrrolidone tends not to be gelled during the positive electrode processing of the positive electrode active material powder. Since positive electrode processing becomes easier, it is preferable. In addition, the charge / discharge cycle characteristics tend to be improved, which is preferable.
  • the average particle size is a particle size at which the cumulative curve is 50% in a cumulative curve in which the particle size distribution is obtained on a volume basis and the total volume is 100%. It means a volume-based cumulative 50% diameter (D50).
  • the particle size distribution can be obtained from the frequency distribution and cumulative volume distribution curve measured with a laser scattering particle size distribution measuring device.
  • powder is water
  • the particle size distribution is measured by sufficiently dispersing in a medium by sonication or the like (for example, using Nikkiso Microtrac HRA (X-100)).
  • the average particle diameter may be referred to as average particle diameter (D50) or D50.
  • D10 represents the particle size at the point where the cumulative curve becomes 10%
  • D90 represents the particle size at the point where the cumulative curve force S 90%.
  • a method for obtaining a positive electrode for a lithium secondary battery using the 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, black lead, and ketjen black with a binder in the powder of the positive electrode active material of the present invention.
  • the binder is preferably polyvinylidene fluoride, polytetrafluoroethylene, polyamide, carboxymethylcellulose, acrylic resin, or the like.
  • a slurry obtained by dispersing the positive electrode mixture in a dispersion medium such as N-methylpyrrolidone is used as an aluminum foil.
  • a positive electrode active material layer is formed on the positive electrode current collector by coating, drying, and pressing and rolling the positive electrode current collector.
  • the electrolyte contained in the battery electrolyte solution or polymer electrolyte is CIO-CFSO-BF-PF.
  • the electrolyte solution or polymer electrolyte of the battery preferably contains the above-described lithium salt electrolyte in a solvent or solvent-containing polymer at a concentration of 0.22.0 mol / L. Beyond this range, the ionic conductivity decreases and the electrical conductivity of the electrolyte decreases. More preferably 0.5 to 1.5; 5 mol / L is selected. For the separator, porous polyethylene or porous polypropylene film is preferred.
  • a carbonate ester is preferable as the solvent of the electrolyte solution.
  • Carbonates can be either cyclic or chain.
  • the cyclic carbonate include propylene carbonate and ethylene carbonate (EC).
  • the chain carbonate include dimethyl carbonate, jetinorecarbonate (DEC), ethinoremethinorecarbonate, methinorepropinorecarbonate, methyl isopropyl carbonate, 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, charge / discharge cycle characteristics, and charge / discharge efficiency.
  • a gel polymer electrolyte may be obtained by adding the following solute.
  • 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.
  • the carbon material those obtained by pyrolyzing an organic substance 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 copper foil, nickel 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.
  • Example 1 to 3 Example 6, Example 8, Example 10, Example 12, Example 14 and Example 16 are examples of the present invention, and are Example 4, Example 5, Example 7, Example 9, Example 11, Example 13, Examples 15 and 17 are comparative examples.
  • the composite hydroxide powder is dispersed in a 6% by weight sodium persulfate aqueous solution containing 3% by weight of sodium hydroxide, and stirred at 20 ° C for 12 hours, thereby obtaining a nickel-cobalt manganese composite oxide.
  • a hydroxide slurry was synthesized. Further, the composite oxyhydroxide slurry was filtered, washed with water, and then dried to obtain composite oxyhydroxide powder.
  • the composite oxyhydroxide powder had a specific surface area of 9.6 m 2 / g and an average particle size of 10. l ⁇ m.
  • the composite oxyhydroxide powder thus obtained was mixed with a predetermined amount of lithium carbonate powder having an average particle diameter of 20 am, baked at 1000 ° C for 16 hours in an atmosphere with an oxygen concentration of 40 vol%, and then pulverized.
  • a base material made of a composite oxide was obtained.
  • the base material had a similar structure with a rhombohedral system (R-3m).
  • RINT 2100 type manufactured by Rigaku Corporation was used.
  • a number of primary particles aggregated to form secondary particles it was found that a number of primary particles aggregated to form secondary particles, and the shape was roughly spherical or elliptical. .
  • an X-ray diffraction spectrum was obtained using an X-ray diffractometer (RINT 2100, manufactured by Rigaku Corporation).
  • RINT 2100 X-ray diffractometer
  • the press density of the particles was 2.7 g / cm 3 .
  • the titanium contained in the entire surface-modified lithium-containing composite oxide particle was 0.001 in atomic ratio with respect to the total of nickel, manganese and cobalt.
  • the lithium ion elution amount was 0.21 mol%.
  • the surface-modified lithium-containing composite oxide particles, acetylene black, and polyvinylidene fluoride powder are mixed at a weight ratio of 90/5/5, and ⁇ -methylpyrrolidone is added to produce a slurry, and the thickness is increased.
  • One side coating was applied to 20 m aluminum foil using a doctor blade. Dry and roll press roll three times to make a positive electrode sheet for lithium batteries.
  • a material obtained by punching the positive electrode sheet is used as the positive electrode, a metal lithium foil having a thickness of 500 m is used as the negative electrode, nickel foil 20 in is used as the negative electrode current collector, and the separator is used as the separator.
  • a porous polypropylene with a thickness of 25 m is used, and the electrolyte contains 1M LiPF /
  • the positive electrode active material lg at 25 ° C with a load current of 30 mA.
  • the battery was charged to 3V and discharged to 2.5V at a load current of 30mA for the positive electrode active material lg to determine the initial discharge capacity. Further, this battery was subsequently subjected to a charge / discharge cycle test 30 times.
  • the initial weight capacity density of the positive electrode active material at 2.5 ° C. and 2.5 4 ⁇ 3 V was 159 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 98.5%.
  • the same operation was performed except that the charge voltage was changed to 4.3 V power, 4.5 V, and the charge / discharge cycle test was performed 25 times.
  • the initial weight capacity density of the positive electrode active material at 5 V was 175 mAh / g, and the capacity retention rate after 25 charge / discharge cycles was 94.9%.
  • the other battery was charged at 4.3 V and 4.5 V for 10 hours, disassembled in an argon glove box, and the charged positive electrode sheet was taken out. After washing the sheet, it was punched out to a diameter of 3 mm, sealed in an aluminum capsule with EC, and heated at a rate of 5 ° C / min with a scanning differential calorimeter to measure the heat generation start temperature.
  • the heat generation start temperature in the heat generation curve of the 4.3V charge product was 233 ° C
  • that of the 4.5V charge was 198 ° C.
  • a thium-containing composite oxide was synthesized.
  • the obtained surface-modified lithium-containing composite oxide particles were measured for X-ray diffraction vectors in the same manner as in Example 1.
  • 2 ⁇ 65.1 ⁇ 1.
  • the half value width of the diffraction peak of (110) plane was 0.226 °.
  • the press density of the particles was 2.69 g / cm 3 .
  • titanium contained in the entire surface-modified lithium-containing composite oxide particle had an atomic ratio of 0.005 with respect to the total of nickel, manganese, and cobalt.
  • the lithium ion elution amount was filed with 0 - 29 mol 0/0.
  • the surface-modified lithium-containing composite oxide has a surface layer.
  • the presence of carbon compounds with carbon double bonds Furthermore, as shown in Fig. 2, the decomposition reaction of titanium lactate progressed from 300 ° C to 450 ° C and the decomposition was almost complete at 500 ° C.
  • Example 2 Furthermore, from these facts, the presence of a carbon compound in the surface layer of the surface-modified lithium-containing composite oxide particles synthesized by heat treatment at 350 ° C. in Example 2 was very strong. In addition, it was proved that the carbon compound was a partial thermal decomposition product of the carbon-containing titanium complex used as a raw material.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 159 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 98.3%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 175 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 95.1%.
  • the heat generation start temperature of the heat generation curve of the 4V charged product is 235 ° C.
  • the heat generation starting temperature of the 5V charged product was 200 ° C.
  • a thium-containing composite oxide was synthesized.
  • the obtained surface-modified lithium-containing composite oxide particles were measured for X-ray diffraction vectors in the same manner as in Example 1.
  • the press density of this particle is 2 It was 69 g / cm 3 .
  • titanium contained in the entire surface-modified lithium-containing composite oxide particles had an atomic ratio of 0.01 with respect to the total of nickel, manganese and cobalt.
  • the surface-modified lithium-containing composite oxide particles obtained were measured for the atomic ratio (Ti / N) of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1.
  • Ti / N 3 ⁇ 30.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 157 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 98.2%. It was.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V is 173 mA h / g, and the capacity retention rate after 25 charge / discharge cycles is 95.1%. there were.
  • the heat generation start temperature of the heat generation curve of the 4V charged product is 234 ° C.
  • the heat generation start temperature of the 5V rechargeable product was 201 ° C.
  • Lithium with the composition of the base material Li (Ni Co Mn) O as in Example 1 Li (Ni Co Mn) O as in Example 1
  • Containing composite oxide was synthesized.
  • the average particle diameter of the base material is 10.
  • ⁇ ⁇ ⁇ ⁇ D10 is 5.3 m
  • D 90 force is 3.5 m
  • the specific surface area is 0.49 m 2 / g.
  • the powder consisted of particles forming particles.
  • an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2100 type, manufactured by Rigaku Corporation).
  • RINT 2100 type manufactured by Rigaku Corporation
  • the press density was 2.70 g / cm 3 .
  • the lithium-containing composite oxide is carbon. Including a compound having an oxygen double bond, it was possible to understand.
  • Example 1 Using the lithium-containing composite oxide particles corresponding to the base material described above, a positive electrode sheet was prepared, a battery was assembled, and evaluated in the same manner as in Example 1.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 160 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 95.0%.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 175 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 91.0%. .
  • the heat generation start temperature of the 4.3V charge product is 232 ° C
  • the 4.5V charge product The onset temperature of 199 ° C was 199 ° C.
  • a thium-containing composite oxide was synthesized.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 160 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 95.2%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 173 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 91.2%. there were.
  • the heat generation start temperature of the heat generation curve of the 4V charged product is 234 ° C.
  • the heat generation starting temperature of the 5V charged product was 201 ° C.
  • the cobalt content is 61.0% by weight of cobalt hydroxide 197. 18 g, Mizusani ⁇ Anoreminiumu 0 ⁇ 16g, and Mizusani ⁇ magnesium 0 ⁇ 12 ⁇ , ⁇ area mosquito 1. 2m 2 / g lithium carbonate powder is mixed with 75.91g, calcined at 990 ° C for 14 hours in an oxygen-containing atmosphere, and pulverized to contain Li (Co Al Mg) 0 containing Li
  • a composite oxide was obtained as a base material.
  • the surface-modified lithium-containing composite oxide particles obtained were measured for the atomic ratio (Ti / N) of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1.
  • Ti / N l. 26.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 157 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 99.8%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V is 184 mA h / g, and the capacity retention rate after 25 charge / discharge cycles is 97.0%. there were.
  • the heat generation start temperature of the heat generation curve of the 4V charged product is 158 ° C.
  • the heat generation starting temperature of the 5V charged product was 146 ° C.
  • a lithium-containing composite oxide having a composition of 0. 997 0. 001 0. 001 0. 001 2 was obtained.
  • the lithium-containing composite oxide has an average particle diameter of 10.3 111,010 mosquitoes. 4 111,090 mosquito 15.4 111 a specific surface area of 0. 26m 2 / g, there is a shape of the particles in a substantially spherical It was.
  • the X-ray diffraction spectrum was measured for the obtained lithium-containing composite oxide particles in the same manner as in Example 1.
  • the press density of the particles was 3.09 g / cm 3 .
  • Titanium contained in the entire lithium-containing composite oxide particles was 0.001 in atomic ratio with respect to the total of cobalt, aluminum, magnesium and titanium.
  • the elution amount of lithium ions was 0 ⁇ 10 mol%.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 159 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 96.9%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V is 185 mA h / g, and the capacity retention rate after 25 charge / discharge cycles is 83.0%. there were.
  • the heat generation start temperature in the heat generation curve of the 3V charged product is 155 ° C.
  • the heat generation start temperature of the 5V rechargeable product was 145 ° C.
  • the above Al-Mg solution was added to 196.62 g of oxyhydroxide cobalt having an average particle size of 12. O ⁇ m and a cobalt content of 60.3% by weight, and the mixture was immersed and mixed at 120 ° C for 4 hours. By drying, an oxycobalt hydroxide powder containing aluminum and magnesium was obtained.
  • a massive lithium-containing composite oxide was obtained as a base material.
  • magnesium hydroxide was dispersed in 50 g of water, and 0.14 g of citrate was added in small portions and dissolved with stirring.
  • 0.06 g of an aqueous solution of titanium lactate having a titanium content of 8.2% by weight was added, and an aqueous solution containing magnesium and titanium having a pH of 2.5 ( Mg—Ti aqueous solution) was prepared.
  • 100 g of the base material was immersed in the Mg-Ti aqueous solution and then slowly mixed to obtain a mixed powder. Further, the mixed powder was dried at 120 ° C. for 4 hours to obtain magnesium titanium complex-impregnated particles.
  • the dried complex-impregnated particles are heated in an oxygen-containing atmosphere at 400 ° C for 12 hours, the average particle size is 12.
  • Q n D10 is 6.8 111, 090 force is 0 m, and the specific surface area is 0.30 m. 2 / g of substantially spherical surface-modified lithium-containing composite oxide particles were obtained.
  • the surface-modified lithium-containing composite oxide particles obtained were measured for the atomic ratio (Ti / N) of the surface of the lithium-containing composite oxide particles by XPS analysis in the same manner as in Example 1.
  • Ti / N l.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 151 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 99.5%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 178 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 95.2%.
  • the heat generation start temperature of the heat generation curve of the 4V charged product is 159 ° C.
  • the heat onset temperature of the 5V rechargeable product was 147 ° C.
  • Example 9 Magnesium hydroxide (0.06 g) was dispersed in 50 g of water, and 0.14 g of citrate was added and dissolved with stirring to prepare an aqueous Mg solution having a pH of 4.0.
  • Lithium-containing composite having the composition of Li (Co Al Mg) O synthesized in Example 8
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 151 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 99.0%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 180 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 92.5%.
  • the heat generation start temperature of the heat generation curve of the 3V charged product is 154 ° C.
  • the heat onset temperature of the 5V rechargeable product was 144 ° C.
  • a predetermined amount of lithium carbonate powder was mixed with the composite oxyhydroxide powder obtained in Example 1, and calcined and ground in the same manner as in Example 1 to obtain Li (Ni Co Mn) O as the base material.
  • a lithium-containing composite oxide having a composition was synthesized.
  • the lithium ion elution amount is 0 ⁇ 38 mol 0 /.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 157 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 98.5%. .
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V is 173 mA h / g, and the capacity retention rate after 25 charge / discharge cycles is 94.5%. there were.
  • the heat generation start temperature of the heat generation curve of the 3V charged product is 231 ° C.
  • the heat generation start temperature of the 5V rechargeable product was 200 ° C.
  • Example 11 Lithium with the composition of the base material Li (Ni Co Mn) O as in Example 10.
  • a complex oxide containing selenium was synthesized.
  • the average particle size of the base material is 10. 8 111, 010 is 6. l ⁇ m, D90 force is 1 m, and the specific surface area is 0.47 m 2 / g. Many primary particles aggregate to form secondary particles. It was the powder which consisted of the particle
  • the press density was 2.70 g / cm 3 .
  • Example 1 Using the lithium-containing composite oxide particles corresponding to the base material described above, a positive electrode sheet was prepared, a battery was assembled, and evaluated in the same manner as in Example 1.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 159 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 94.9%.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.5 V was 174 mA h / g, and the capacity retention rate after 25 charge / discharge cycles was 90.0%.
  • the heat generation start temperature of the 4.3V charge product is 230 ° C
  • the 4.5V charge product The onset temperature of 198 ° C was 198 ° C.
  • the pH of the slurry in the reaction vessel is 11 ⁇ 0, and the temperature is adjusted to 30 ° C by mixing a sulfate mixed solution containing nickel sulfate, cobalt sulfate and manganese sulfate, an aqueous ammonium sulfate solution, and an aqueous sodium hydroxide solution.
  • a sulfate mixed solution containing nickel sulfate, cobalt sulfate and manganese sulfate, an aqueous ammonium sulfate solution, and an aqueous sodium hydroxide solution Each was continuously fed to the reaction vessel with stirring so that the temperature became 50 ° C.
  • the amount of liquid in the reaction system was adjusted by the overflow method, and the overflowed coprecipitation slurry was filtered, washed with water, and then dried at 80 ° C. to obtain a nickel cobalt manganese composite hydroxide powder.
  • the composite hydroxide powder is dispersed in a 6% by weight sodium persulfate aqueous solution containing 3% by weight sodium hydroxide, and stirred at 20 ° C. for 12 hours.
  • Ngan composite oxyhydroxide slurry was synthesized. Further, the composite oxyhydroxide slurry was filtered, washed with water, and then dried to obtain composite oxyhydroxide powder.
  • the composite oxyhydroxide powder had a specific surface area of 9.4 m 2 / g and an average particle size of 9.5 m.
  • a predetermined amount of lithium carbonate powder having an average particle diameter of 20 am was mixed with the composite oxyhydroxide powder thus obtained, and calcined in an oxygen-containing atmosphere at 970 ° C for 12 hours, followed by pulverization. From a lithium-containing composite oxide having the composition Li (Ni Co Mn) O
  • the X-ray diffraction spectrum was measured in the same manner as in Example 1.
  • 2 ⁇ 65.1 ⁇ 1.
  • the half value width of the diffraction peak of (110) plane was 0.139 °.
  • the press density of the particles was 2.65 g / cm 3 .
  • titanium contained in the entire surface-modified lithium-containing composite oxide particles had an atomic ratio of 0.001 with respect to the total of nickel, manganese and cobalt.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 165 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 97.5%. .
  • the temperature at a rate of 5 ° C / min was measured with a scanning differential calorimeter and the heat generation start temperature was measured.
  • the heat generation start temperature in the heat generation curve of the 4.3V charged product was 202 ° C.
  • the base material has an average particle size of 8.9 111, D10 of 5. O ⁇ m, D9 0 of 14.9 m, and a specific surface area of 0.50 m 2 / g.
  • the powder consisted of particles forming particles.
  • an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2100 type, manufactured by Rigaku Corporation).
  • RINT 2100 type manufactured by Rigaku Corporation
  • the press density was 2.69 g / cm 3 .
  • lithium-containing composite oxide particles as the base material were subjected to surface elemental analysis by XPS analysis in the same manner as in Example 1, titanium was not detected.
  • Example 1 Using the lithium-containing composite oxide particles corresponding to the base material described above, a positive electrode sheet was prepared, a battery was assembled, and evaluated in the same manner as in Example 1.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 168 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 96.0%.
  • the heat generation start temperature of the 4.3V charged product was 201 ° C.
  • the composite hydroxide powder is dispersed in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide and stirred at 20 ° C. for 12 hours, whereby a nickel cobalt manganese composite oxide is obtained.
  • a hydroxide slurry was synthesized. Further, the composite oxyhydroxide slurry was filtered, washed with water, and then dried to obtain composite oxyhydroxide powder.
  • the composite oxyhydroxide powder had a specific surface area of 9.4 m 2 / g and an average particle size of 9.5 m.
  • a predetermined amount of lithium carbonate powder having an average particle size of 20 ⁇ m was mixed with the composite oxyhydroxide powder thus obtained, and calcined in an oxygen-containing atmosphere at 990 ° C. for 12 hours, and then pulverized to obtain Li ( Ni Co Mn) O-containing lithium composite oxide
  • the lithium ion elution amount was filed in 0.35 mol 0/0.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 153 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 97.3%. .
  • the heat generation start temperature of the heat generation curve of the 4.3V charged product was 191 ° C.
  • a complex oxide containing selenium was synthesized.
  • the base material has an average particle size of 9.9 111, D10 of 4.9 111, D 90 force of 3.9 m, and a specific surface area of 0.40 m 2 / g. It was a powder composed of particles formed.
  • an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2100 type, manufactured by Rigaku Corporation).
  • RINT 2100 type manufactured by Rigaku Corporation
  • the press density was 2.75 g / cm 3 .
  • lithium-containing composite oxide particles as the base material were subjected to surface elemental analysis by XPS analysis in the same manner as in Example 1, titanium was not detected.
  • Example 1 Using the lithium-containing composite oxide particles corresponding to the base material described above, a positive electrode sheet was prepared, a battery was assembled, and evaluated in the same manner as in Example 1.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 155 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 96.0%.
  • a sulfuric acid mixed solution containing nickel sulfate, cobalt sulfate, and manganese sulfate, an aqueous solution of ammonium sulfate, and an aqueous solution of sodium hydroxide were prepared so that the pH of the slurry in the reaction vessel was 11
  • the amount of liquid in the reaction system was adjusted by the overflow method, and the overflowed coprecipitation slurry was filtered, washed with water, and then dried at 80 ° C. to obtain a nickel cobalt manganese composite hydroxide powder.
  • the composite hydroxide powder is dispersed in a 6% by weight aqueous sodium persulfate solution containing 3% by weight of sodium hydroxide, and stirred at 20 ° C. for 12 hours, whereby a nickel cobalt manganese composite oxide is obtained.
  • a hydroxide slurry was synthesized. Further, the composite oxyhydroxide slurry was filtered, washed with water, and then dried to obtain composite oxyhydroxide powder.
  • the composite oxyhydroxide powder had a specific surface area of 10.8 m 2 / g and an average particle size of 9. O ⁇ rn.
  • a predetermined amount of lithium carbonate powder having an average particle diameter of 20 ⁇ m was mixed with the composite oxyhydroxide powder obtained in this way, calcined in an oxygen-containing atmosphere at 950 ° C. for 12 hours, and then pulverized to obtain Li ( From a lithium-containing composite oxide having the composition Ni Co Mn) O
  • the lithium ion elution amount was filed in 0.37 mol 0/0.
  • An electrode and a battery were prepared and evaluated in the same manner as in Example 1 except that the positive electrode sheet was prepared using the surface-modified lithium-containing composite oxide.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 140 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 97.8%. .
  • the heat generation start temperature of the 4.3V rechargeable product was 240 ° C.
  • a complex oxide containing selenium was synthesized.
  • the base material has an average particle size of 8.5 111, 010 parts um, D 90 force of 4.2 m, and a specific surface area of 0.62 m 2 / g. It was a powder consisting of the formed particles.
  • an X-ray diffraction spectrum was obtained using an X-ray diffraction apparatus (RINT 2100 type, manufactured by Rigaku Corporation).
  • RINT 2100 type manufactured by Rigaku Corporation
  • the press density was 2.55 g / cm 3 .
  • lithium-containing composite oxide particles as the base material were subjected to surface elemental analysis by XPS analysis in the same manner as in Example 1, titanium was not detected.
  • Example 1 Using the lithium-containing composite oxide particles that correspond to the base material, as in Example 1, A positive electrode sheet was prepared, a battery was assembled and evaluated.
  • the initial weight capacity density of the positive electrode active material at 25 ° C. and 2.5 to 4.3 V was 142 mAh / g, and the capacity retention rate after 30 charge / discharge cycles was 96.1%.
  • the heat generation start temperature of the 4.3V charged product was 239 ° C.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery comprising a lithium-containing composite oxide particle having a high operating voltage, high discharge capacity, and excellent charge / discharge cycle characteristics without deteriorating high safety
  • a method for producing a positive electrode active material and a nonaqueous electrolyte secondary battery using the positive electrode active material are provided.

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Abstract

L'invention concerne un matériau actif d'électrode positive hautement sûr dont les caractéristiques de cycle de charge/décharge sont excellentes, tout en ayant une capacité de décharge élevée même à une tension de fonctionnement élevée. L'invention concerne également un procédé de production d'un tel matériau actif d'électrode positive, et une batterie secondaire à électrolyte non aqueux comprenant un tel matériau actif d'électrode positive. L'invention concerne de manière spécifique un matériau actif d'électrode positive pour des batteries secondaires à électrolyte non aqueux qui se compose d'une particule d'oxyde complexe contenant du lithium modifié en surface représenté par la formule générale suivante : LipNxMyO2 (dans lequel N représente au moins un élément choisi dans le groupe constitué par Co, Mn et Ni ; M représente un élément choisi parmi un groupe constitué par des métaux de transition autres que l'élément N, des métaux alcalino-terreux et l'aluminium ; et 0,9 ≤ p ≤ 1,1, 0,9 ≤ x < 1,1, 0 ≤ y ≤0,3). Le matériau actif d'électrode positive pour des batteries secondaires à électrolyte non aqueux est en outre caractérisé par le fait que la couche de surface de celui-ci contient du titane, et le rapport atomique du contenu de titane au contenu de l'élément N dans une plage de 5 nm à partir de la surface n'est pas inférieur à 0,6.
PCT/JP2007/064606 2006-07-26 2007-07-25 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux et procédé de production de celui-ci Ceased WO2008013208A1 (fr)

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JP4915488B1 (ja) * 2011-03-28 2012-04-11 住友金属鉱山株式会社 ニッケルマンガン複合水酸化物粒子とその製造方法、非水系電解質二次電池用正極活物質とその製造方法、および非水系電解質二次電池
CN104779387A (zh) * 2015-04-14 2015-07-15 哈尔滨工程大学 锂离子电池LiNi1-x-yCoxAlyO2材料的制备方法
JP5828989B2 (ja) * 2013-05-17 2015-12-09 三井金属鉱業株式会社 リチウム二次電池用正極活物質
CN109478645A (zh) * 2016-07-14 2019-03-15 三井金属矿业株式会社 全固体型锂二次电池用正极活性物质
JP2021042098A (ja) * 2019-09-11 2021-03-18 日本化学工業株式会社 改質リチウムコバルト系複合酸化物粒子の製造方法
WO2022097653A1 (fr) * 2020-11-05 2022-05-12 日本化学工業株式会社 Procédé de production de particules d'oxyde composite de lithium-nickel-manganèse-cobalt modifiées
JP2022075569A (ja) * 2020-11-05 2022-05-18 日本化学工業株式会社 改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法
CN116490997A (zh) * 2020-11-05 2023-07-25 日本化学工业株式会社 改性锂镍锰钴复合氧化物颗粒的制造方法
WO2023237967A1 (fr) * 2022-06-08 2023-12-14 株式会社半導体エネルギー研究所 Batterie secondaire

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JP7252298B2 (ja) 2020-11-05 2023-04-04 日本化学工業株式会社 改質リチウムニッケルマンガンコバルト複合酸化物粒子の製造方法
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