WO2012057289A1 - リチウムイオン二次電池用正極活物質、正極、電池、及び製造方法 - Google Patents
リチウムイオン二次電池用正極活物質、正極、電池、及び製造方法 Download PDFInfo
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- WO2012057289A1 WO2012057289A1 PCT/JP2011/074867 JP2011074867W WO2012057289A1 WO 2012057289 A1 WO2012057289 A1 WO 2012057289A1 JP 2011074867 W JP2011074867 W JP 2011074867W WO 2012057289 A1 WO2012057289 A1 WO 2012057289A1
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- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [MnO2]n-, e.g. Li(CoxMn1-x)O2, Li(MyCoxMn1-x-y)O2
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- 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
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Definitions
- the present invention relates to a positive electrode active material for a lithium ion secondary battery, a positive electrode, a lithium ion secondary battery, and a method for producing a positive electrode active material for a lithium ion secondary battery.
- Lithium ion secondary batteries are widely used in portable electronic devices such as mobile phones and notebook computers.
- a positive electrode active material for a lithium ion secondary battery a composite oxide of lithium and a transition metal or the like such as LiCoO 2 , LiNiO 2 , LiNi 0.8 Co 0.2 O 2 , LiMnO 4 is used.
- a lithium ion secondary battery using LiCoO 2 as a positive electrode active material and a carbon such as a lithium alloy, graphite, or carbon fiber as a negative electrode can obtain a high voltage of 4V, so that it has a high energy density. Widely used.
- discharge capacity the discharge capacity per unit mass or the characteristic that the discharge capacity does not decrease after repeated charge / discharge cycles
- the composition ratio of Li element and transition metal element containing a lithium transition metal composite oxide having an ⁇ -NaFeO 2 type crystal structure is Li 1 + 1 / 3x Co 1-x-
- the transition metal contains a large amount of manganese element, and the electrolytic solution in which the manganese element is decomposed by charging at a high voltage Elution is easy when contacted. For this reason, the crystal structure of the positive electrode active material becomes unstable, and in particular, the cycle characteristics due to repeated charge and discharge are insufficient.
- Patent Document 2 describes that the stability of the crystal structure is improved by incorporating Al, Ti, Mg, and B elements into the crystal structure of the lithium composite oxide in order to improve such cycle characteristics. Has been. However, such a crystal structure has a problem that the discharge capacity per unit mass is lowered, and is insufficient as a material that achieves both high discharge capacity and cycle characteristics.
- Patent Document 3 describes a positive electrode active material for a non-aqueous electrolyte secondary battery in which a large amount of Zr element is present in the surface layer. Patent Document 3 describes that the cycle characteristics are excellent even at a high operating voltage of 4.5 V, but the initial discharge capacity is 191 mAh / g or less, and a sufficient discharge capacity can be obtained. There wasn't.
- the present invention provides a positive electrode active material for a lithium ion secondary battery, a positive electrode, a lithium ion secondary battery, and a positive electrode active material for a lithium ion secondary battery, which are excellent in cycle characteristics and rate characteristics even when charged at a high voltage. Provide a method.
- the gist of the present invention is as follows. [1] Including Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is 1. with respect to the total molar amount of the transition metal element). More than twice.) It is characterized by comprising particles (II) in which the oxide (I) of at least one metal element selected from Zr, Ti, and Al is unevenly distributed on the surface of the lithium-containing composite oxide. Positive electrode active material for lithium ion secondary battery. [2] The molar amount of at least one metal element selected from the group consisting of Zr, Ti, and Al is 0.0001 to 0.05 times the total molar amount of transition metal elements of the lithium-containing composite oxide.
- composition (1) A composition in which a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is dissolved in a solvent. [6] The production method according to [5], wherein the heating is performed at 200 to 600 ° C.
- the lithium-containing composite oxide and the composition are added to the lithium-containing composite oxide stirring the contact between the lithium-containing composite oxide and the composition (1).
- the compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is zirconium carbonate ammonium, zirconium zirconium halide, titanium lactate, titanium lactate ammonium salt, aluminum lactate, and basic lactic acid.
- the production method according to any one of [5] to [10], wherein the lithium-containing composite oxide is represented by the following general formula (1). Li (Li x Mn y Me z ) O p F q (1) However, Me is at least one element selected from the group consisting of Co and Ni. 0.1 ⁇ x ⁇ 0.25, 0.5 ⁇ y / (y + z) ⁇ 0.8, x + y + z 1, 1.9 ⁇ p ⁇ 2.1, and 0 ⁇ q ⁇ 0.1. [12] The contact between the lithium-containing composite oxide and the composition (1) is performed by spraying the composition onto the lithium-containing composite oxide by a spray coating method. [5] to [11] The manufacturing method as described in any one of these.
- a positive electrode for a lithium ion secondary battery comprising the positive electrode active material for a lithium ion secondary battery according to any one of [1] to [4], a conductive material, and a binder.
- a lithium ion secondary battery including the positive electrode, the negative electrode, and a nonaqueous electrolyte according to [13].
- the positive electrode active material of the present invention is excellent in cycle characteristics and rate characteristics even when charged at a high voltage.
- the positive electrode and the lithium ion secondary battery of the present invention are excellent in cycle characteristics and rate characteristics even when charged at a high voltage.
- the manufacturing method of the present invention can manufacture a positive electrode active material, a positive electrode, and a lithium ion secondary battery that are excellent in cycle characteristics and rate characteristics even when charged at a high voltage.
- the positive electrode active material of the present invention contains Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the molar amount of Li element is the total molar amount of the transition metal element)
- composition ratio of Li element to the total molar amount of the transition metal element is preferably 1.25 to 1.75 in order to further increase the discharge capacity per unit mass, and is 1.25 to 1.65. More preferably, it is particularly preferably 1.40 to 1.55.
- the transition metal element only needs to contain at least one element selected from the group consisting of Ni, Co, and Mn, more preferably contains at least Mn element, and all elements of Ni, Co, and Mn It is especially preferable that it contains.
- the lithium-containing composite oxide (I) may contain a metal element other than Ni, Co, Mn, and Li (hereinafter referred to as other metal element). As other metal elements, elements such as Cr, Fe, Al, Ti, Zr, and Mg may be included.
- the lithium-containing composite oxide is preferably a compound represented by the following general formula (1).
- Me is at least one element selected from the group consisting of Co, Ni, Cr, Fe, Al, Ti, Zr, and Mg.
- 0.09 ⁇ x ⁇ 0.3, 0.4 ⁇ y / (y + z) ⁇ 0.8, x + y + z 1, 1.9 ⁇ p ⁇ 2.1, 0 ⁇ q ⁇ 0.1.
- Co, Ni, and Cr are preferable, and Co and Ni are particularly preferable.
- 0.1 ⁇ x ⁇ 0.25 is preferable, 0.11 ⁇ x ⁇ 0.22 is more preferable, 0.5 ⁇ y / (y + z) ⁇ 0.8 is preferable, and 0 .55 ⁇ y / (y + z) ⁇ 0.75 is more preferable.
- the molar ratio of Co to Ni is preferably 0 to 1.5, more preferably 0.1 to 1, and particularly preferably 0.2 to 0.8.
- Me may contain a small amount of at least one element selected from the group consisting of Al, Ti, Mg, Zr, La, Ce, Cr, and Fe.
- the small amount means 0.001 to 0.05 times the total molar amount of Mn, Co and Ni.
- lithium-containing composite oxide Li (Li 0.13 Ni 0.26 Co 0.09 Mn 0.52 ) O 2 , Li (Li 0.13 Ni 0.22 Co 0.09 Mn 0 .56 ) O 2 , Li (Li 0.13 Ni 0.17 Co 0.17 Mn 0.53 ) O 2 , Li (Li 0.15 Ni 0.17 Co 0.13 Mn 0.55 ) O 2 , Li (Li 0.16 Ni 0.17 Co 0.08 Mn 0.59 ) O 2 , Li (Li 0.17 Ni 0.17 Co 0.17 Mn 0.49 ) O 2 , Li (Li 0.17 Ni 0.21 Co 0.08 Mn 0.54 ) O 2 , Li (Li 0.17 Ni 0.14 Co 0.14 Mn 0.55 ) O 2 , Li (Li 0.18 Ni 0.12 Co 0 .12 Mn 0.58) O 2, Li ( i 0.18 Ni 0.16 Co 0.12 Mn 0.54 ) O 2, Li (Li 0.20 Ni 0.12 Co 0.08 Mn 0.60) O 2, Li (Li 0.20 Ni 0.12
- the lithium-containing composite oxide is preferably in the form of particles, and the average particle diameter D50 is preferably 3 to 30 ⁇ m, more preferably 4 to 25 ⁇ m, and particularly preferably 5 to 20 ⁇ m.
- the average particle diameter D50 is a particle diameter at a point at which the cumulative curve is 50% in a cumulative curve obtained by obtaining a particle size distribution on a volume basis and setting the total volume to 100%. It means the diameter (D50).
- the particle size distribution is obtained from a frequency distribution and a cumulative volume distribution curve measured with a laser scattering particle size distribution measuring apparatus.
- the particle size is measured by sufficiently dispersing the powder in an aqueous medium by ultrasonic treatment or the like and measuring the particle size distribution (for example, using a laser diffraction / scattering particle size distribution measuring device Partica LA-950VII manufactured by HORIBA). Used).
- the specific surface area of the lithium-containing composite oxide is preferably 0.3 ⁇ 10m 2 / g, more preferably 0.5 ⁇ 5m 2 / g, 1 ⁇ 4m 2 / g is particularly preferred. When the specific surface area is 0.3 to 10 m 2 / g, the capacity is high and a dense positive electrode layer can be formed.
- the lithium-containing composite oxide in the present invention preferably has a layered rock salt type crystal structure (space group R-3m).
- XRD X-ray diffraction
- the oxide (I) in the present invention is preferably an inactive compound with the decomposition product in order to prevent contact with the decomposition product generated by decomposition of the electrolyte generated by charging (oxidation reaction) at a high voltage.
- the oxide (I) is an oxide of at least one metal element selected from the group consisting of Zr, Ti, and Al. Specific examples include ZrO 2, TiO 2, Al 2 O 3.
- the oxide (I) may be a metal single oxide, a composite oxide, or a mixture of a plurality of single oxides. Examples of the composite oxide include ZrTiO 4 , MgAl 2 O 4 , LiAiO 2 and the like.
- Examples of the single oxide mixture include a mixture of ZrO 2 and MgO, a mixture of ZrO 2 and TiO 2, a mixture of Al 2 O 3 and ZrO 2 , and the like. Since oxide (I) is easy to obtain a uniform film and is chemically stable, ZrO 2 and Al 2 O 3 are preferable, and Al 2 O 3 is particularly preferable.
- the particles (II) in the present invention are those in which the oxide (I) is unevenly distributed on the surface of the lithium-containing composite oxide.
- being unevenly distributed means that the oxide (I) is contained more on the surface than the center of the lithium-containing composite oxide.
- the oxide (I) is unevenly distributed on the surface of the lithium-containing composite oxide.
- the cross section is polished, and the X-ray microanalyzer analysis method ( It can be evaluated by elemental mapping with EPMA).
- the oxide (I) is the center of the lithium-containing composite oxide (here, the center is a portion not in contact with the surface of the lithium-containing composite oxide, and the average distance from the surface is the longest). On the other hand, it can be confirmed that there is more in the range of 100 nm from the surface.
- the ratio of the oxide (I) in the particles (II) can be measured by dissolving the positive electrode active material in an acid and performing ICP (high frequency inductively coupled plasma) measurement.
- ICP high frequency inductively coupled plasma
- the ratio of the oxide (I) in the particles (II) is excellent in the cycle maintenance rate
- the molar amount of at least one metal element selected from the group consisting of Zr, Ti, and Al in the oxide (I) is The amount is preferably 0.005 to 0.04 times, more preferably 0.007 to 0.035 times, and more preferably 0.01 to 0.005 times the molar amount of the transition metal element of the lithium-containing composite oxide. It is particularly preferable that the ratio is 03 times.
- the shape of the oxide (I) unevenly distributed on the surface of the lithium-containing composite oxide should be evaluated by an electron microscope such as SEM (scanning electron microscope) or TEM (transmission electron microscope). Can do.
- the shape of the oxide (I) may be in the form of particles, a film, or a lump, but is particularly preferably a film.
- the average particle size of the oxide (I) is preferably from 0.1 to 100 nm, more preferably from 0.1 to 50 nm, and particularly preferably from 0.1 to 30 nm.
- the average particle diameter of the oxide (I) is an average particle diameter of the particles covering the surface of the lithium-containing composite oxide, which is observed with an electron microscope such as SEM or TEM.
- the oxide (I) may be unevenly distributed on at least a part of the surface of the lithium-containing composite oxide, but it is particularly preferable that the oxide (I) is unevenly distributed on the entire surface of the lithium-containing composite oxide.
- the surface means a surface or a surface layer.
- the oxide (1) is present in a larger amount in the surface layer, preferably 0.02 ⁇ m from the surface or the surface than the inside of the lithium-containing composite oxide particles. Since the positive electrode active material of the present invention uses a lithium-containing composite oxide having a high lithium ratio, the discharge capacity is large.
- the elution of Mn element is suppressed, and even when the charge / discharge cycle is performed at a high voltage (especially 4.5 V or more), the capacity is hardly lowered and the cycle characteristics are excellent.
- the method for producing a positive electrode active material for a lithium ion secondary battery of the present invention includes Li element and at least one transition metal element selected from the group consisting of Ni, Co, and Mn (provided that the mole of Li element) The amount is more than 1.2 times the total molar amount of the transition metal element.)
- the lithium-containing composite oxide is brought into contact with and heated by contacting the lithium-containing composite oxide with the following composition (1).
- This is a method for obtaining a positive electrode active material for a lithium ion secondary battery comprising particles (II) in which an oxide (I) of at least one metal element selected from the group consisting of Zr, Ti, and Al is unevenly distributed on the surface of the object. .
- Composition (1) A composition in which a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is dissolved in a solvent.
- a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is dissolved in a solvent.
- the lithium-containing composite oxide the above-described lithium-containing composite oxide can be used, and the preferred embodiment is also the same.
- a method for producing a lithium-containing composite oxide As a method for producing a lithium-containing composite oxide, a method of mixing and baking a precursor of a lithium-containing composite oxide obtained by a coprecipitation method and a lithium compound, a hydrothermal synthesis method, a sol-gel method, a dry mixing method, an ion The exchange method etc. are mentioned, but since the discharge metal capacity is excellent by mixing the contained transition metal elements uniformly, the coprecipitation composition (precursor of lithium-containing composite oxide) obtained by the coprecipitation method and the lithium compound The method of mixing and baking is preferable.
- the composition (1) is a composition in which a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is dissolved in a solvent.
- a compound containing a Zr element zirconium carbonate ammonium, zirconium ammonium halide, and zirconium acetate are preferable, and zirconium carbonate ammonium or zirconium ammonium halide is more preferable.
- titanium lactate ammonium salt titanium lactate, titanium diisopropoxybis (triethanolaminate), peroxotitanium, titanium peroxocitrate complex is preferable, and titanium lactate or titanium lactate ammonium salt is more preferable.
- titanium lactate or titanium lactate ammonium salt is more preferable.
- Al element aluminum acetate, aluminum oxalate, aluminum citrate, aluminum lactate, basic aluminum lactate, and aluminum maleate are preferable, and aluminum lactate or basic aluminum lactate is particularly preferable.
- the reason why the above ammonium ammonium carbonate, zirconium ammonium halide, titanium lactate, titanium lactate ammonium salt, aluminum lactate or basic aluminum lactate is preferable is that when these compounds are used, the metal element concentration in the composition (1) is increased.
- the metal element oxide (I ) Is easily coated uniformly.
- a Li-rich lithium-containing composite oxide in which the molar amount of Li element exceeds 1.2 with respect to the total molar amount of the transition metal element is liable to increase the pH of the composition (1).
- the composition (1) does not produce a precipitate even when the amount is as described above.
- the reason why the above ammonium zirconium carbonate, ammonium zirconium halide, titanium lactate, titanium lactate ammonium salt, aluminum lactate or basic aluminum lactate is preferable is that (A) an aqueous solution containing these compounds is combined with lithium-containing composite oxide Since the aqueous solution at the time of contacting with an object does not become excessively acidic, dissolution of the lithium-containing composite oxide can be suppressed. Further, (B) no harmful gas such as nitrogen oxide gas is generated during heating. (C) There is also an advantage that components other than Zr, Ti, or Al, which are target elements, which are harmful to battery performance, such as sulfate radicals, do not remain in the particles (II) after heating.
- a solvent containing water is preferable from the viewpoint of stability and reactivity of the compound containing a metal element, a mixed solvent of water and a water-soluble alcohol and / or polyol is more preferable, and water is particularly preferable.
- the water-soluble alcohol include methanol, ethanol, 1-propanol, and 2-propanol.
- the polyol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, butanediol, and glycerin.
- the total content of the water-soluble alcohol and polyol contained in the solvent is preferably 0 to 20% by mass, more preferably 0 to 10% by mass with respect to the total amount of each solvent (total amount of solvent).
- the solvent is only water, it is particularly preferable because it is excellent in terms of safety, environment, handling, and cost.
- the composition (1) may contain a pH adjusting agent.
- a pH adjuster those that volatilize or decompose upon heating are preferable. Specifically, organic acids such as acetic acid, citric acid, lactic acid, and formic acid, and ammonia are preferable.
- the pH of the composition (1) is preferably 3 to 12, more preferably 3.5 to 12, and particularly preferably 4 to 10. When the pH is in the above range, there is little elution of Li element from the lithium-containing composite oxide when the lithium-containing composite oxide is brought into contact with the composition (1), and impurities such as a pH adjuster are present. Since there are few, it is easy to obtain a favorable battery characteristic.
- the heating temperature is preferably 40 ° C to 80 ° C, particularly preferably 50 ° C to 70 ° C.
- the concentration of the compound containing a metal element contained in the composition (1) used in the present invention is preferably higher because it is necessary to remove the solvent by heating in a later step. However, when the concentration is too high, the viscosity is increased, the uniform mixing property of the composition (1) with another element source forming the positive electrode active material is reduced, and the lithium-containing composite oxide contains Ni. Since the composition (1) is less likely to penetrate into the Ni element source, the concentration of the compound containing the metal element contained in the composition (1) is preferably 1 to 30% by mass in terms of the oxide (I) of the metal element. 4 to 20% by mass is particularly preferable.
- a contact method between the lithium-containing composite oxide and the composition (1) for example, a spray coating method or a wet method can be applied, and a method of spraying the composition (1) onto the lithium-containing composite oxide by the spray coating method is particularly preferable. preferable.
- the wet method since the solvent needs to be removed by filtration or evaporation after contact, the process becomes complicated.
- the spray coating method the process is simple and the oxide (I) can be uniformly attached to the surface of the lithium-containing composite oxide.
- the amount of the composition (1) to be brought into contact with the lithium-containing composite oxide is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and particularly preferably 3 to 30% by weight with respect to the lithium-containing composite oxide. . If the ratio of the composition (1) is within the above range, the oxide (I) can be uniformly adhered to the surface of the lithium-containing composite oxide, and the composition (1) is spray-coated on the lithium-containing composite oxide. At this time, the lithium-containing composite oxide is not agglomerated and easy to stir.
- the composition (1) is added to the stirred lithium-containing composite oxide, and the lithium-containing composite oxide and the composition (1) are mixed, thereby forming the composition. It is preferable to contact (1) with the lithium-containing composite oxide.
- a drum mixer or a solid-air low shear stirring device can be used as the stirring device. By contacting the composition (1) and the lithium-containing composite oxide while stirring and mixing, particles (II) in which the oxide (I) is unevenly distributed on the surface of the lithium-containing composite oxide can be obtained.
- the lithium-containing composite oxide is brought into contact with the composition (1) and heated.
- a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is efficiently oxidized ( I) and volatile impurities such as water and organic components can be removed.
- Heating is preferably performed in an oxygen-containing atmosphere.
- the heating temperature is preferably 200 to 600 ° C, more preferably 250 to 550 ° C, and particularly preferably 350 to 550 ° C. If the heating temperature is 200 ° C. or higher, a compound containing at least one metal element selected from the group consisting of Zr, Ti, and Al is likely to change to oxide (I), and further volatile impurities such as residual moisture are present. Less and does not adversely affect cycle characteristics. If the heating temperature is within the above range, the reaction between the oxide (I) and lithium or a lithium-containing composite oxide is difficult to proceed, and the cycle characteristics are improved because the oxide (I) is unevenly distributed on the surface of the lithium-containing composite oxide. To do.
- the heating time is preferably 0.1 to 24 hours, more preferably 0.5 to 18 hours, and particularly preferably 1 to 12 hours.
- the positive electrode for lithium ion secondary batteries of this invention contains said positive electrode active material, a electrically conductive material, and a binder.
- the positive electrode for a lithium ion secondary battery is formed by forming a positive electrode active material layer containing the positive electrode active material of the present invention on a positive electrode current collector (positive electrode surface).
- the positive electrode for a lithium ion secondary battery is, for example, a slurry or kneaded product by dissolving the positive electrode active material, the conductive material and the binder of the present invention in a solvent, dispersing in a dispersion medium, or kneading with a solvent. And the prepared slurry or kneaded material is supported on the positive electrode current collector plate by coating or the like.
- the conductive material examples include carbon black such as acetylene black, graphite, and ketjen black.
- binders fluorine-containing resins such as polyvinylidene fluoride and polytetrafluoroethylene, polyolefins such as polyethylene and polypropylene, polymers having unsaturated bonds such as styrene / butadiene rubber, isoprene rubber and butadiene rubber, and copolymers thereof, Examples thereof include acrylic acid-based polymers such as acrylic acid copolymers and methacrylic acid copolymers, and copolymers thereof.
- the lithium ion secondary battery of this invention contains said positive electrode for lithium ion secondary batteries, a negative electrode, and a nonaqueous electrolyte.
- the negative electrode is formed by forming a negative electrode active material layer containing a negative electrode active material on a negative electrode current collector. For example, it can be produced by preparing a slurry by kneading a negative electrode active material with an organic solvent, and applying, drying, and pressing the prepared slurry to a negative electrode current collector.
- the negative electrode current collector plate for example, a metal foil such as a nickel foil or a copper foil can be used.
- the negative electrode active material may be any material that can occlude and release lithium ions.
- lithium metal, lithium alloy, lithium compound, carbon material, periodic table 14 and group 15 metal oxides, carbon Compounds, silicon carbide compounds, silicon oxide compounds, titanium sulfide, boron carbide compounds, and the like can be used.
- lithium alloys and lithium compounds composed of lithium and a metal capable of forming an alloy or compound with lithium
- the carbon material include non-graphitizable carbon, artificial graphite, natural graphite, pyrolytic carbon, pitch coke, needle coke, petroleum coke, and other cokes, graphite, glassy carbon, phenolic resin, and furan resin.
- An organic polymer compound fired body, carbon fiber, activated carbon, carbon black or the like obtained by firing and carbonizing the above at an appropriate temperature can be used.
- the group 14 metal of the periodic table is, for example, silicon or tin, and most preferably silicon.
- materials that can occlude and release lithium ions at a relatively low potential include, for example, oxides such as iron oxide, ruthenium oxide, molybdenum oxide, tungsten oxide, titanium oxide, and tin oxide, and other nitrides. It can be used similarly.
- nonaqueous electrolyte it is preferable to use a nonaqueous electrolytic solution in which an electrolyte salt is dissolved in a nonaqueous solvent.
- a nonaqueous electrolyte one prepared by appropriately combining an organic solvent and an electrolyte can be used. Any organic solvent may be used as long as it is used in this type of battery. For example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxy.
- Ethane, ⁇ -butyrolactone, diethyl ether, sulfolane, methyl sulfolane, acetonitrile, acetic acid ester, butyric acid ester, propionic acid ester and the like can be used.
- cyclic carbonates such as propylene carbonate and chain carbonates such as dimethyl carbonate and diethyl carbonate.
- organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- nonaqueous electrolyte a solid electrolyte containing an electrolyte salt, a polymer electrolyte, a solid or gel electrolyte in which an electrolyte is mixed or dissolved, and the like can be used.
- the solid electrolyte may be any material having lithium ion conductivity.
- any of an inorganic solid electrolyte and a polymer solid electrolyte can be used.
- lithium nitride, lithium iodide, or the like can be used.
- the polymer solid electrolyte an electrolyte salt and a polymer compound that dissolves the electrolyte salt can be used.
- an ether polymer such as poly (ethylene oxide) or a crosslinked product thereof, a poly (methacrylate) ester, an acrylate, or the like is used alone or in a molecule, or a mixture thereof is used. be able to.
- the matrix of the gel electrolyte may be any matrix that absorbs the non-aqueous electrolyte and gels, and various polymers can be used.
- the polymer material used for the gel electrolyte for example, fluorine-based polymers such as poly (vinylidene fluoride) and poly (vinylidene fluoride-co-hexafluoropropylene) can be used.
- a polymer material used for the gel electrolyte for example, polyacrylonitrile and a copolymer of polyacrylonitrile can be used.
- an ether polymer such as polyethylene oxide, a copolymer of polyethylene oxide, and a crosslinked product thereof can be used.
- the copolymerization monomer include polypropylene oxide, methyl methacrylate, butyl methacrylate, methyl acrylate, and butyl acrylate.
- any electrolyte salt used in various electrolytes as described above can be used as long as it is used in this type of battery.
- the electrolyte salt for example, LiClO 4 , LiPF 6 , LiBF 4 , CH 3 SO 3 Li, LiCl, LiBr, or the like can be used.
- the shape of the lithium ion secondary battery of the present invention can be appropriately selected from coin shapes, sheet shapes (film shapes), folded shapes, wound bottomed cylindrical shapes, button shapes, and the like according to applications. .
- the mother liquor was placed in a 2 L baffled glass reaction vessel, heated to 50 ° C. with a mantle heater, and a pH adjusting solution was added so that the pH was 11.0.
- the raw material solution was added at a rate of 5.0 g / min
- the ammonia source solution was added at a rate of 1.0 g / min
- a composite hydroxide of nickel, cobalt, and manganese was added. Precipitated.
- the pH adjusting solution was added so as to keep the pH in the reaction vessel at 11.0.
- nitrogen gas was flowed at a flow rate of 0.5 L / min in the reaction tank so that the precipitated hydroxide was not oxidized. Further, the liquid was continuously extracted so that the amount of the liquid in the reaction tank did not exceed 2 L.
- the composition of the lithium-containing composite oxide of the obtained example is Li 1.2 (Ni 0.172 Co 0.156 Mn 0.672 ) 0.8 O 2 .
- the average particle diameter D50 of the lithium-containing composite oxides of the examples was 5.9 ⁇ m, and the specific surface area measured using the BET (Brunauer, Emmett, Teller) method was 2.6 m 2 / g.
- Example 1 Aluminum content was prepared Al solution by adding distilled water 2.98g to 8.5% by weight of a basic aluminum lactate solution 7.02g terms of Al 2 O 3 (composition (1)). 1.0 g of the composition (1) is sprayed and added to 10 g of the lithium-containing composite oxide of the example, and the lithium-containing composite oxide of the example and the composition (1) are mixed and brought into contact with each other. It was. Next, the obtained mixture was dried at 90 ° C. for 2 hours and then heated at 450 ° C. for 8 hours in an oxygen-containing atmosphere, whereby particles (II) in which the oxide (I) of Al element was unevenly distributed on the surface of the lithium-containing composite oxide The positive electrode active material (A) of Example 1 consisting of was obtained.
- Aluminum which is the metal element (coating material) of the composition (1) contained in the positive electrode active material (A) is based on the total of nickel, cobalt and manganese which are transition metal elements of the lithium-containing composite oxide of the example.
- the molar ratio (coating amount) is ⁇ (number of moles of Al) / (total number of moles of Ni, Co, Mn) ⁇ 0.013.
- Examples 2 to 4 The same procedure as in Example 1 was carried out except that the amount of the composition (1) to be sprayed was changed to 0.5 g, 1.5 g, and 2.0 g, respectively, and the surface of the lithium-containing composite oxide had an oxide of Al element (I) Positive electrode active materials (B) to (D) composed of particles (II) with uneven distribution were obtained.
- Aluminum that is a metal element (coating material) of the composition (1) contained in the positive electrode active materials (B) to (D) is nickel, cobalt, or manganese that is a transition metal element of the lithium-containing composite oxide of the example.
- the molar ratio (covering amount) is ⁇ (number of moles of Al) / (total number of moles of Ni, Co, Mn) ⁇ , 0.006, 0.019, and 0.025, respectively.
- the cross sections of the powders of the obtained positive electrode active materials (B) to (D) were embedded with resin and polished with fine particles of cerium oxide, and the particle cross sections of the positive electrode active materials (B) to (D) were subjected to Al mapping with EPMA. As a result, more Al was detected on the outer surface of the particle than inside the particle.
- Example 5 To 6.97 g of an aqueous solution of ammonium zirconium carbonate (chemical formula: (NH 4 ) 2 [Zr (CO 3 ) 2 (OH) 2 ]) having a zirconium content of 20.7 mass% in terms of ZrO 2 , 3.03 g of distilled water was added. A Zr aqueous solution (Composition (2)) was prepared. Next, 1.5 g of the composition (2) is added by spraying to 10 g of the lithium-containing composite oxide of the example being stirred, and the lithium-containing composite oxide and the composition (2) of the example are added. And contacting with mixing. Next, the obtained mixture was dried at 90 ° C. for 2 hours and then heated at 450 ° C.
- ammonium zirconium carbonate chemical formula: (NH 4 ) 2 [Zr (CO 3 ) 2 (OH) 2 ]
- Zirconium which is a metal element (coating material) of the composition (2) contained in the positive electrode active material (E), is based on the total of nickel, cobalt, and manganese, which are transition metal elements of the lithium-containing composite oxide of the example.
- the molar ratio (coating amount) is ⁇ (number of moles of Zr) / (total number of moles of Ni, Co, Mn) ⁇ 0.019.
- a cross section of the obtained positive electrode active material (E) powder was embedded in resin and polished with fine cerium oxide particles, and the positive electrode active material (E) particle cross section was subjected to Zr mapping with EPMA (X-ray microanalyzer). As a result, more Zr could be detected on the outer surface of the particle than inside the particle.
- EPMA X-ray microanalyzer
- Example 6 Except that the amount of the composition (2) to be sprayed was changed to 1.0 g and 2.0 g, respectively, the same procedure as in Example 5 was performed, and the oxide (I) of Zr element was unevenly distributed on the surface of the lithium-containing composite oxide.
- Positive electrode active materials (F) to (G) comprising particles (II) were obtained.
- Zirconium, which is a metal element (coating material) of the composition (2) contained in the positive electrode active materials (F) to (G) is composed of nickel, cobalt, and manganese, which are transition metal elements of the lithium-containing composite oxide of the example.
- the molar ratio (coating amount) is ⁇ (molar number of Zr) / (total molar number of Ni, Co, Mn) ⁇ 0.013 and 0.025, respectively.
- the cross section of the obtained positive electrode active material (F) to (G) powder was embedded in resin, polished with fine cerium oxide particles, and the positive electrode active material (F) to (G) particle cross section was subjected to Zr mapping with EPMA. As a result, more Zr could be detected on the outer surface of the particle than inside the particle.
- composition (6) Distilled water (7.92 g) was added to indium nitrate trihydrate (2.08 g) to prepare an aqueous Sr solution (composition (6)). Except for adding 1.0 g of the composition (1) to the lithium-containing composite oxide of the example instead of spraying 2.0 g of the composition (3) to (6), the example was added. 1 to obtain positive electrode active materials (I) to (L) comprising particles (II) in which the oxide (I) of Sr, B, Mg, or In is unevenly distributed on the surface of the lithium-containing composite oxide. It was.
- the positive electrode active material As the positive electrode active material, the positive electrode active materials (A) to (L) of Examples 1 to 7 and Comparative Examples 1 to 5 were used, respectively, and the positive electrode active material, acetylene black (conductive material), and polyvinylidene fluoride (binder) was mixed with a polyvinylidene fluoride solution containing 12.1% by mass (solvent N-methylpyrrolidone), and N-methylpyrrolidone was further added to prepare a slurry.
- the positive electrode active material, acetylene black, and polyvinylidene fluoride were in a mass ratio of 80/12/8.
- a punched positive electrode sheet of Examples 1 to 7 and Comparative Examples 1 to 4 is used as a positive electrode, a metal lithium foil with a thickness of 500 ⁇ m is used as a negative electrode, and a stainless steel with a thickness of 1 mm is used as a negative electrode current collector.
- the lithium battery of Comparative Example 1 was assembled in an argon glove box.
- the positive electrode sheet was prepared by the above method, and the positive electrode sheets of Examples 1 to 3 and Comparative Example 1 were obtained.
- the cycle maintenance rate of the lithium battery of the comparative example is 72% or less, whereas the cycle maintenance rate of the lithium battery of the example exceeds 75%.
- a high cycle retention rate was obtained when the coating material was Al.
- a positive electrode active material, a positive electrode, and a lithium ion secondary battery for a lithium ion secondary battery that are small and light, have a high discharge capacity per unit mass, and have excellent cycle characteristics. It can be used for electronic devices such as telephones and in-vehicle batteries.
Abstract
Description
しかしながら、Li元素の遷移金属元素に対する組成比(モル比)が1以上である正極活物質では、遷移金属にマンガン元素が多く含まれ、該マンガン元素が高電圧での充電によって分解した電解液と接触すると溶出しやすい。このため、正極活物質の結晶構造が不安定となり、特に充放電の繰り返しによるサイクル特性が不充分であった。
[1]Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物の表面に、Zr、Ti、およびAlから選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなることを特徴とするリチウムイオン二次電池用の正極活物質。
[2]Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素のモル量が、前記リチウム含有複合酸化物の遷移金属元素の総モル量に対して0.0001~0.05倍である[1]に記載の正極活物質。
[3]前記金属元素の酸化物(I)が、ZrO2、TiO2、およびAl2O3からなる群から選ばれる少なくとも一種である[1]または[2]に記載の正極活物質。
Li(LixMnyMez)OpFq (1)
ただし、Meは、CoおよびNiからなる群から選ばれる少なくとも一種の元素である。0.1<x<0.25、0.5≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1である。
[5]Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物と、下記組成物(1)とを接触させて、加熱することにより、前記リチウム含有複合酸化物の表面にZr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなるリチウムイオン二次電池用正極活物質を得ることを特徴とする、リチウムイオン二次電池用正極活物質の製造方法。
組成物(1):Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素を含む化合物を溶媒に溶解させた組成物。
[6]前記加熱を200~600℃で行う[5]に記載の製造方法。
[7]前記組成物(1)の溶媒が、水である[5]または[6]に記載の製造方法。
[8]前記組成物(1)のpHが、3~12である[5]~[7]のいずれか一項に記載の製造方法。
[9]前記リチウム含有複合酸化物と、前記組成物(1)との接触を、撹拌しているリチウム含有複合酸化物に該組成物を添加して、前記リチウム含有複合酸化物と該組成物とを混合することにより行う、[5]~[8]のいずれか一項に記載の製造方法。
[10]前記Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素を含む化合物が、炭酸ジルコニウムアンモニウム、ハロゲン化ジルコニウムアンモニウム、チタンラクテート、チタンラクテートアンモニウム塩、乳酸アルミニウム、および塩基性乳酸アルミニウムからなる群から選ばれる少なくとも一種の化合物である、[5]~[9]のいずれか一項に記載の製造方法。
[11]前記リチウム含有複合酸化物が、下記一般式(1)で表される、[5]~[10]のいずれか一項に記載の製造方法。
Li(LixMnyMez)OpFq (1)
ただし、Meは、CoおよびNiからなる群から選ばれる少なくとも一種の元素である。0.1<x<0.25、0.5≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1である。
[12]前記リチウム含有複合酸化物と、前記組成物(1)との接触を、スプレーコート法によって該組成物を前記リチウム含有複合酸化物に噴霧することにより行う、[5]~[11]のいずれか一項に記載の製造方法。
[14][13]に記載の正極と負極と非水電解質とを含むリチウムイオン二次電池。
本発明の正極活物質は、Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物の表面に、Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなることを特徴とする。
本発明におけるリチウム含有複合酸化物は、Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含むものであって、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超{(Li元素のモル量/遷移金属元素の総モル量)>1.2}である。Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超であれば、単位質量あたりの放電容量を向上させることができる。
リチウム含有複合酸化物(I)は、Ni、Co、Mn、およびLi以外の金属元素(以下、他の金属元素という。)を含んでいてもよい。他の金属元素としては、Cr、Fe、Al、Ti、Zr、Mg等の元素を含んでいてもよい。具体的には、リチウム含有複合酸化物として、下記一般式(1)で表される化合物が好ましい。
一般式(1)において、Meは、Co、Ni、Cr、Fe、Al、Ti、Zr、Mgからなる群から選ばれる少なくとも一種の元素である。一般式(1)においては、0.09<x<0.3、0.4≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1である。Meとしては、Co、Ni、Crが好ましく、Co、Niが特に好ましい。一般式(1)においては、0.1<x<0.25が好ましく、0.11<x<0.22がより好ましく、0.5≦y/(y+z)≦0.8が好ましく、0.55≦y/(y+z)≦0.75がより好ましい。
一般式(1)において、Meは、CoおよびNiからなる群から選ばれる少なくとも一種の元素であり、0.1<x<0.25、0.5≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1であるのが好ましい。Meは、CoおよびNiであるのが特に好ましい。かかる場合、Niに対するCoのモル比(Co/Ni)は、0~1.5が好ましく、0.1~1がより好ましく、0.2~0.8が特に好ましい。また、MeがCoおよびNiに加え、Al,Ti,Mg,Zr,La,Ce,Cr,およびFeからなる群から選ばれる少なくとも1種の元素を少量含んでもよい。ここで少量とは、Mn,CoおよびNiの総モル量に対して、0.001~0.05倍であることを意味する。
本発明におけるリチウム含有複合酸化物は、層状岩塩型結晶構造(空間群R-3m)をとるものであることが好ましい。また、本発明におけるリチウム含有複合酸化物は、遷移金属元素に対するLi元素の比率が高いため、XRD(X線回折)測定では層状Li2MnO3と同様に2θ=20~25°の範囲にピークが観察される。
本発明における酸化物(I)は、高電圧での充電(酸化反応)によって生じる電解質の分解によって生じた分解物との接触を防ぐため、分解物と不活性な化合物であることが好ましい。
酸化物(I)は、Zr、Ti、Alからなる群から選ばれる少なくとも一種の金属元素の酸化物である。具体的には、ZrO2、TiO2、Al2O3が挙げられる。
また、酸化物(I)は、金属の単独酸化物であっても、複合酸化物であっても、複数の単独酸化物の混合物であってもよい。複合酸化物としては、ZrTiO4、MgAl2O4、LiAiO2等が例示される。単独酸化物の混合物としては、ZrO2およびMgOの混合物、ZrO2およびTiO2の混合物、Al2O3およびZrO2の混合物等が例示される。
酸化物(I)は、均一な被膜が得られやすく、化学的に安定であることから、ZrO2、Al2O3が好ましく、Al2O3が特に好ましい。
本発明における粒子(II)は、上記リチウム含有複合酸化物の表面に上記酸化物(I)が偏在するものである。ここで、偏在するとは、前記酸化物(I)がリチウム含有複合酸化物の中心よりも表面に多く含まれていることをいう。前記粒子(II)において、酸化物(I)がリチウム含有複合酸化物の表面に偏在していることは、例えば、粒子(II)を切断した後に断面を研磨し、X線マイクロアナライザー分析法(EPMA)で元素マッピングを行うことにより評価することができる。該評価方法によって、前記酸化物(I)がリチウム含有複合酸化物の中心(ここで、中心とは、リチウム含有複合酸化物の表面に接していない部分をいい、表面からの平均距離が最長である部分であるのが好ましい。)に対して、表面から100nmの範囲により多く存在することが確認できる。
本発明の正極活物質は、リチウム比率の高いリチウム含有複合酸化物を用いているため放電容量が大きい。また、本発明の正極活物質は、リチウム含有複合酸化物の表面にZr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素の酸化物(I)が偏在している粒子(II)からなるものであるため、特にMn元素の溶出が抑制され、高電圧(特に4.5V以上)で充放電サイクルを行っても容量の低下が少なく、サイクル特性に優れる。
本発明のリチウムイオン二次電池用正極活物質の製造方法としては、Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物と、下記組成物(1)とを接触させて、加熱することにより前記リチウム含有複合酸化物の表面にZr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなるリチウムイオン二次電池用正極活物質を得る方法である。
リチウム含有複合酸化物としては、上記のリチウム含有複合酸化物を用いることができ、好ましい態様も同様である。
Zr元素を含む化合物としては、炭酸ジルコニウムアンモニウム、ハロゲン化ジルコニウムアンモニウム、酢酸ジルコニウムが好ましく、炭酸ジルコニウムアンモニウムまたはハロゲン化ジルコニウムアンモニウムがより好ましい。
Al元素を含む化合物としては、酢酸アルミニウム、シュウ酸アルミニウム、クエン酸アルミニウム、乳酸アルミニウム、塩基性乳酸アルミニウム、およびマレイン酸アルミニウムが好ましく、乳酸アルミニウムまたは塩基性乳酸アルミニウムが特に好ましい。
また、上記炭酸ジルコニウムアンモニウム、ハロゲン化ジルコニウムアンモニウム、チタンラクテート、チタンラクテートアンモニウム塩、乳酸アルミニウム、または塩基性乳酸アルミニウムが好ましい理由としては、さらに、(A)これらの化合物を含む水溶液をリチウム含有複合酸化物と接触させる際の水溶液が過度に酸性になることがないので、リチウム含有複合酸化物の溶解を抑止できる。また、(B)加熱する際に、有害なガス、例えば窒素酸化物ガス等の発生がない。および、(C)加熱後に、目的とする元素であるZr,Ti,またはAl以外の、電池性能発現に有害な成分、例えば硫酸根が、粒子(II)に残留しない利点もある。
組成物(1)のpHとしては、3~12が好ましく、3.5~12がより好ましく、4~10が特に好ましい。pHが上記の範囲にあれば、リチウム含有複合酸化物と組成物(1)とを接触させたときのリチウム含有複合酸化物からのLi元素の溶出が少なく、また、pH調整剤等の不純物が少ないため良好な電池特性が得られやすい。
本発明のリチウムイオン二次電池用正極は、上記の正極活物質、導電材、およびバインダーを含む。
リチウムイオン二次電池用正極は、正極集電体上(正極表面)に、本発明の正極活物質を含有する正極活物質層が形成されてなる。リチウムイオン二次電池用正極は、例えば、本発明の正極活物質、導電材およびバインダーを、溶媒に溶解させるか、分散媒に分散させるか、又は溶媒と混練することによって、スラリー又は混錬物を調製し、調製したスラリー又は混錬物を正極集電板に塗布等により担持させることによって、製造することができる。
バインダーとしては、ポリフッ化ビニリデン、ポリテトラフルオロエチレン等のフッ素系樹脂、ポリエチレン、ポリプロピレン等のポリオレフィン、スチレン・ブタジエンゴム、イソプレンゴム、ブタジエンゴム等の不飽和結合を有する重合体およびその共重合体、アクリル酸共重合体、メタクリル酸共重合体等のアクリル酸系重合体およびその共重合体等が挙げられる。
本発明のリチウムイオン二次電池は、上記のリチウムイオン二次電池用正極、負極、および非水電解質を含む。
負極は、負極集電体上に、負極活物質を含有する負極活物質層が形成されてなる。例えば、負極活物質を有機溶媒と混錬することによってスラリーを調製し、調製したスラリーを負極集電体に塗布、乾燥、プレスすることによって、製造することができる。
負極活物質としては、リチウムイオンを吸蔵、放出可能な材料であればよく、例えば、リチウム金属、リチウム合金、リチウム化合物、炭素材料、周期表14、15族の金属を主体とする酸化物、炭素化合物、炭化ケイ素化合物、酸化ケイ素化合物、硫化チタンおよび炭化ホウ素化合物等を用いることができる。
炭素材料としては、例えば、難黒鉛化性炭素、人造黒鉛、天然黒鉛、熱分解炭素類、ピッチコークス、ニードルコークス、石油コークス等のコークス類、グラファイト類、ガラス状炭素類、フェノール樹脂やフラン樹脂等を適当な温度で焼成し炭素化した有機高分子化合物焼成体、炭素繊維、活性炭、カーボンブラック類等を用いることができる。
周期表14族の金属としては、例えば、ケイ素あるいはスズであり、最も好ましくはケイ素である。また、比較的低い電位でリチウムイオンを吸蔵、放出可能な材料であれば、例えば、酸化鉄、酸化ルテニウム、酸化モリブデン、酸化タングステン、酸化チタン、酸化スズ等の酸化物およびその他の窒化物等も同様に用いることができる。
非水電解液としては、有機溶媒と電解質とを適宜組み合わせて調製されたものを用いることができる。有機溶媒としては、この種の電池に用いられるものであればいずれも使用可能であり、例えば、プロピレンカーボネート、エチレンカーボネート、ジエチルカーボネート、ジメチルカーボネート、1,2-ジメトキシエタン、1,2-ジエトキシエタン、γ-ブチロラクトン、ジエチルエーテル、スルホラン、メチルスルホラン、アセトニトリル、酢酸エステル、酪酸エステル、プロピオン酸エステル等を用いることができる。特に、電圧安定性の点からは、プロピレンカーボネート等の環状カーボネート類、ジメチルカーボネート、ジエチルカーボネート等の鎖状カーボネート類を使用することが好ましい。また、このような有機溶媒は、1種類を単独で用いてもよく、2種類以上を混合して用いてもよい。
固体電解質としては、リチウムイオン伝導性を有する材料であればよく、例えば、無機固体電解質および高分子固体電解質のいずれをも用いることができる。
高分子固体電解質としては、電解質塩と該電解質塩を溶解する高分子化合物を用いることができる。そして、この高分子化合物としては、ポリ(エチレンオキサイド)や同架橋体などのエーテル系高分子、ポリ(メタクリレート)エステル系、アクリレート系等を、単独あるいは分子中に共重合、または混合して用いることができる。
また、酸化還元反応に対する安定性の観点により、上記した高分子のうち、特にフッ素系高分子を用いることが好ましい。
本発明のリチウムイオン二次電池の形状は、コイン型、シート状(フィルム状)、折り畳み状、巻回型有底円筒型、ボタン型等の形状を、用途に応じて適宜選択することができる。
硫酸ニッケル(II)六水和物140.6g、硫酸コバルト(II)七水和物131.4g、硫酸マンガン(II)五水和物482.2gに蒸留水1245.9gを加えて均一に溶解させて原料溶液とした。硫酸アンモニウム79.2に蒸留水320.8gを加えて均一に溶解させてアンモニア源溶液とした。硫酸アンモニウム79.2に蒸留水1920.8gを加えて均一に溶解させて母液とした。水酸化ナトリウム400gに蒸留水600gを加えて均一に溶解させてpH調整液とした。
ICPで前駆体のニッケル、コバルト、マンガンの含有量を測定したところ、それぞれ11.6質量%、10.5質量%、42.3質量%であった(モル比でニッケル:コバルト:マンガン=0.172:0.156:0.672)。
アルミニウム含量がAl2O3換算で8.5質量%の塩基性乳酸アルミニウム水溶液7.02gに蒸留水2.98gを加えてAl水溶液(組成物(1))を調製した。
実施例のリチウム含有複合酸化物10gに対して、組成物(1)の1.0gを噴霧して添加し、実施例のリチウム含有複合酸化物と組成物(1)とを混合させながら接触させた。次いで、得られた混合物を90℃で2時間乾燥した後に酸素含有雰囲気下450℃で8時間加熱し、リチウム含有複合酸化物の表面にAl元素の酸化物(I)が偏在する粒子(II)からなる実施例1の正極活物質(A)を得た。
(実施例2~4)
噴霧する組成物(1)の量をそれぞれ0.5g、1.5g、2.0gとした以外は実施例1と同様に行い、リチウム含有複合酸化物の表面にAl元素の酸化物(I)が偏在する粒子(II)からなる正極活物質(B)~(D)を得た。
正極活物質(B)~(D)に含まれる組成物(1)の金属元素(被覆材料)であるアルミニウムは、実施例のリチウム含有複合酸化物の遷移金属元素であるニッケル、コバルト、マンガンの合計に対して、それぞれモル比(被覆量)で{(Alのモル数)/(Ni、Co、Mnの合計モル数)}0.006、0.019、0.025である。得られた正極活物質(B)~(D)の粉末の断面を樹脂で包埋し、酸化セリウム微粒子で研磨し、正極活物質(B)~(D)の粒子断面をEPMAでAlマッピングを行なった結果、粒子内部より、粒子外表面により多くのAlを検出できた。
ジルコニウム含量がZrO2換算で20.7質量%の炭酸ジルコニウムアンモニウム(化学式:(NH4)2[Zr(CO3)2(OH)2])水溶液6.97gに、蒸留水3.03gを加えて、Zr水溶液(組成物(2))を調製した。
次に、撹拌している実施例のリチウム含有複合酸化物10gに対して、組成物(2)の1.5gを噴霧して添加し、実施例のリチウム含有複合酸化物と組成物(2)とを混合させながら接触させた。次いで、得られた混合物を90℃で2時間乾燥した後に酸素含有雰囲気下450℃で5時間加熱し、リチウム含有複合酸化物の表面にZr元素の酸化物(I)が偏在する粒子(II)からなる正極活物質(E)を得た。
正極活物質(E)に含まれる組成物(2)の金属元素(被覆材料)であるジルコニウムは、実施例のリチウム含有複合酸化物の遷移金属元素であるニッケル、コバルト、マンガンの合計に対して、モル比(被覆量)で{(Zrのモル数)/(Ni、Co、Mnの合計モル数)}0.019である。得られた正極活物質(E)の粉末の断面を樹脂で包埋し、酸化セリウム微粒子で研磨し、正極活物質(E)の粒子断面をEPMA(X線マイクロアナライザ)でZrマッピングを行なった結果、粒子内部より、粒子外表面により多くのZrを検出できた。
噴霧する組成物(2)の量をそれぞれ1.0g、2.0g、とした以外は実施例5と同様に行い、リチウム含有複合酸化物の表面にZr元素の酸化物(I)が偏在する粒子(II)からなる正極活物質(F)~(G)を得た。
正極活物質(F)~(G)に含まれる組成物(2)の金属元素(被覆材料)であるジルコニウムは、実施例のリチウム含有複合酸化物の遷移金属元素であるニッケル、コバルト、マンガンの合計に対して、それぞれモル比(被覆量)で{(Zrのモル数)/(Ni、Co、Mnの合計モル数)}0.013、0.025である。得られた正極活物質(F)~(G)の粉末の断面を樹脂で包埋し、酸化セリウム微粒子で研磨し、正極活物質(F)~(G)の粒子断面をEPMAでZrマッピングを行なった結果、粒子内部より、粒子外表面により多くのZrを検出できた。
実施例のリチウム含有複合酸化物に対して被覆処理は行わず、正極活物質(H)とした。
(比較例2~5)
硝酸ストロンチウム1.24gに、蒸留水8.76gを加えて、Sr水溶液(組成物(3))を調製した。
ホウ酸0.36g、蒸留水9.64gを加えて、B水溶液(組成物(4))を調製した。
硝酸マグネシウム六水和物1.50gに、蒸留水8.50gを加えて、Sr水溶液(組成物(5))を調製した。
硝酸インジウム・三水和物2.08gに、蒸留水7.92gを加えて、Sr水溶液(組成物(6))を調製した。
実施例のリチウム含有複合酸化物に対して、組成物(1)の1.0gを噴霧する代わりに組成物(3)~(6)の2.0gを噴霧して添加した以外は、実施例1と同様に行い、リチウム含有複合酸化物の表面にそれぞれSr、B、Mg、またはInの酸化物(I)が偏在する粒子(II)からなる正極活物質(I)~(L)を得た。
正極活物質として、実施例1~実施例7、比較例1~5の正極活物質(A)~(L)をそれぞれ用い、正極活物質とアセチレンブラック(導電材)とポリフッ化ビニリデン(バインダー)を12.1質量%含むポリフッ化ビニリデン溶液(溶媒N-メチルピロリドン)を混合し、さらにN-メチルピロリドンを添加してスラリーを作製した。正極活物質と、アセチレンブラックと、ポリフッ化ビニリデンは質量比で80/12/8とした。スラリーを厚さ20μmのアルミニウム箔(正極集電体)にドクターブレードを用いて片面塗工した。120℃で乾燥し、ロールプレス圧延を2回行うことによりリチウム電池用の正極となる実施例1~実施例7、比較例1~4の正極体シートを作製した。
前記の実施例1~実施例7、比較例1~4の正極体シートを打ち抜いたものを正極に用い、厚さ500μmの金属リチウム箔を負極に用い、負極集電体に厚さ1mmのステンレス板を使用し、セパレータには厚さ25μmの多孔質ポリプロピレンを用い、さらに電解液には、濃度1(mol/dm3)のLiPF6/EC(エチレンカーボネート)+DEC(ジエチルカーボネート)(1:1)溶液(LiPF6を溶質とするECとDECとの体積比(EC:DEC=1:1)の混合溶液を意味する。)を用いてステンレス製簡易密閉セル型の実施例1~実施例3、比較例1のリチウム電池をアルゴングローブボックス内で組み立てた。
上記の方法により正極体シートの作製を行い、実施例1~実施例3、比較例1の正極体シートを得た。
前記実施例1~実施例7、比較例1~5のリチウム電池について、25℃にて電池評価を行った。
すなわち、正極活物質1gにつき200mAの負荷電流で4.6Vまで充電し、正極活物質1gにつき100mAの負荷電流にて2.5Vまで放電する充放電サイクルを100回繰返した。
この時、3サイクル目の放電容量を4.6V初期容量とする。また、100サイクル目の放電容量/3サイクル目の放電容量をサイクル維持率とする。
実施例1~実施例7、比較例1~5のリチウム電池について、4.6V初期容量、サイクル維持率を表1にまとめる。
なお、2010年10月29日に出願された日本特許出願2010-243914号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物の表面に、Zr、Ti、およびAlから選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなることを特徴とするリチウムイオン二次電池用の正極活物質。
- Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素のモル量が、前記リチウム含有複合酸化物の遷移金属元素の総モル量に対して0.0001~0.05倍である請求項1に記載の正極活物質。
- 前記金属元素の酸化物(I)が、ZrO2、TiO2、およびAl2O3からなる群から選ばれる少なくとも一種である請求項1または2に記載の正極活物質。
- 前記リチウム含有複合酸化物が、下記一般式(1)で表される、請求項1~3のいずれか一項に記載の正極活物質。
Li(LixMnyMez)OpFq (1)
ただし、Meは、CoおよびNiからなる群から選ばれる少なくとも一種の元素である。0.1<x<0.25、0.5≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1である。 - Li元素と、Ni、Co、およびMnからなる群から選ばれる少なくとも一種の遷移金属元素とを含む(ただし、Li元素のモル量が該遷移金属元素の総モル量に対して1.2倍超である。)リチウム含有複合酸化物と、下記組成物(1)とを接触させて、加熱することにより、前記リチウム含有複合酸化物の表面にZr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素の酸化物(I)が偏在する粒子(II)からなるリチウムイオン二次電池用正極活物質を得ることを特徴とする、リチウムイオン二次電池用正極活物質の製造方法。
組成物(1):Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素を含む化合物を溶媒に溶解させた組成物。 - 前記加熱を200~600℃で行う請求項5に記載の製造方法。
- 前記組成物(1)の溶媒が、水である請求項5または6に記載の製造方法。
- 前記組成物(1)のpHが、3~12である請求項5~7のいずれか一項に記載の製造方法。
- 前記リチウム含有複合酸化物と、前記組成物(1)との接触を、撹拌しているリチウム含有複合酸化物に該組成物を添加して、前記リチウム含有複合酸化物と該組成物とを混合することにより行う、請求項5~8のいずれか一項に記載の製造方法。
- 前記Zr、Ti、およびAlからなる群から選ばれる少なくとも一種の金属元素を含む化合物が、炭酸ジルコニウムアンモニウム、ハロゲン化ジルコニウムアンモニウム、チタンラクテート、チタンラクテートアンモニウム塩、乳酸アルミニウム、および塩基性乳酸アルミニウムからなる群から選ばれる少なくとも一種の化合物である、請求項5~9のいずれか一項に記載の製造方法。
- 前記リチウム含有複合酸化物が、下記一般式(1)で表される、請求項5~10のいずれか一項に記載の製造方法。
Li(LixMnyMez)OpFq (1)
ただし、Meは、CoおよびNiからなる群から選ばれる少なくとも一種の元素である。0.1<x<0.25、0.5≦y/(y+z)≦0.8、x+y+z=1、1.9<p<2.1、0≦q≦0.1である。 - 前記リチウム含有複合酸化物と、前記組成物(1)との接触を、スプレーコート法によって該組成物を前記リチウム含有複合酸化物に噴霧することにより行う、請求項5~11のいずれか一項に記載の製造方法。
- 請求項1~4のいずれか一項に記載のリチウムイオン二次電池用の正極活物質と導電材とバインダーとを含むリチウムイオン二次電池用正極。
- 請求項13に記載の正極と負極と非水電解質とを含むリチウムイオン二次電池。
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20150069336A (ko) * | 2013-12-13 | 2015-06-23 | 삼성정밀화학 주식회사 | 양극 활물질 및 이를 포함하는 리튬이차전지 |
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003151548A (ja) | 2001-11-09 | 2003-05-23 | Sony Corp | 正極材料およびそれを用いた電池 |
JP2003234102A (ja) * | 2001-10-17 | 2003-08-22 | Samsung Sdi Co Ltd | リチウム二次電池用正極活物質及びその製造方法 |
WO2007052712A1 (ja) * | 2005-11-02 | 2007-05-10 | Agc Seimi Chemical Co., Ltd. | リチウム含有複合酸化物及びその製造方法 |
WO2007102407A1 (ja) | 2006-03-02 | 2007-09-13 | Agc Seimi Chemical Co., Ltd. | 非水電解質二次電池用正極活物質及びその製造方法 |
JP2009152114A (ja) | 2007-12-21 | 2009-07-09 | Gs Yuasa Corporation | リチウム二次電池用活物質、リチウム二次電池及びその製造方法 |
US20100233550A1 (en) * | 2009-03-16 | 2010-09-16 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
JP2010243914A (ja) | 2009-04-08 | 2010-10-28 | Kyoto Univ | 音響モデル学習装置、音声認識装置、及び音響モデル学習のためのコンピュータプログラム |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4822317B2 (ja) * | 2005-10-03 | 2011-11-24 | Kddi株式会社 | レコメンド方法およびシステムならびにレコメンドプログラムおよびその記憶媒体 |
KR20090082913A (ko) * | 2006-11-08 | 2009-07-31 | 닛산 가가쿠 고교 가부시키 가이샤 | 실리카 알루미나 복합 졸 및 이의 제조방법 |
KR100814826B1 (ko) * | 2006-11-20 | 2008-03-20 | 삼성에스디아이 주식회사 | 리튬 이차 전지 |
EP2219251B1 (en) * | 2007-11-12 | 2014-06-25 | GS Yuasa International Ltd. | Active material for lithium rechargeable battery and lithium rechargeable battery |
WO2009097581A1 (en) * | 2008-01-31 | 2009-08-06 | American International Group, Inc. | Method and system of developing a product |
KR101288973B1 (ko) * | 2011-05-04 | 2013-07-24 | 삼성전자주식회사 | 전극활물질, 그 제조방법 및 이를 채용한 전극 및 리튬전지 |
-
2011
- 2011-10-27 EP EP11836422.3A patent/EP2634846A4/en not_active Withdrawn
- 2011-10-27 WO PCT/JP2011/074867 patent/WO2012057289A1/ja active Application Filing
- 2011-10-27 JP JP2012540946A patent/JP5831457B2/ja active Active
- 2011-10-27 KR KR1020137010446A patent/KR20130139941A/ko active Search and Examination
- 2011-10-27 KR KR1020187037078A patent/KR20190000381A/ko not_active Application Discontinuation
- 2011-10-27 CN CN2011800513789A patent/CN103181006A/zh active Pending
-
2013
- 2013-04-29 US US13/872,676 patent/US20130236788A1/en not_active Abandoned
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003234102A (ja) * | 2001-10-17 | 2003-08-22 | Samsung Sdi Co Ltd | リチウム二次電池用正極活物質及びその製造方法 |
JP2003151548A (ja) | 2001-11-09 | 2003-05-23 | Sony Corp | 正極材料およびそれを用いた電池 |
WO2007052712A1 (ja) * | 2005-11-02 | 2007-05-10 | Agc Seimi Chemical Co., Ltd. | リチウム含有複合酸化物及びその製造方法 |
JP2011181527A (ja) * | 2005-11-02 | 2011-09-15 | Agc Seimi Chemical Co Ltd | リチウム含有複合酸化物 |
WO2007102407A1 (ja) | 2006-03-02 | 2007-09-13 | Agc Seimi Chemical Co., Ltd. | 非水電解質二次電池用正極活物質及びその製造方法 |
JP2009152114A (ja) | 2007-12-21 | 2009-07-09 | Gs Yuasa Corporation | リチウム二次電池用活物質、リチウム二次電池及びその製造方法 |
US20100233550A1 (en) * | 2009-03-16 | 2010-09-16 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
JP2010243914A (ja) | 2009-04-08 | 2010-10-28 | Kyoto Univ | 音響モデル学習装置、音声認識装置、及び音響モデル学習のためのコンピュータプログラム |
Non-Patent Citations (1)
Title |
---|
See also references of EP2634846A4 |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012151084A (ja) * | 2010-12-27 | 2012-08-09 | Gs Yuasa Corp | 非水電解質二次電池用正極活物質、リチウム遷移金属複合酸化物、非水電解質二次電池用正極活物質の製造方法、及び非水電解質二次電池 |
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US10026960B2 (en) | 2013-09-30 | 2018-07-17 | Lg Chem, Ltd. | Cathode active material coating solution for secondary battery and method of manufacturing the same |
US10756338B2 (en) | 2013-09-30 | 2020-08-25 | Lg Chem, Ltd. | Cathode active material for secondary battery and method of manufacturing the same |
KR20150069336A (ko) * | 2013-12-13 | 2015-06-23 | 삼성정밀화학 주식회사 | 양극 활물질 및 이를 포함하는 리튬이차전지 |
KR102152882B1 (ko) * | 2013-12-13 | 2020-09-07 | 삼성에스디아이 주식회사 | 양극 활물질 및 이를 포함하는 리튬이차전지 |
KR20150078177A (ko) * | 2013-12-30 | 2015-07-08 | 삼성정밀화학 주식회사 | 리튬 이차전지용 양극 활물질, 이의 제조 방법 및 이를 포함하는 리튬 이차전지 |
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US10276866B2 (en) | 2014-12-17 | 2019-04-30 | Nissan Motor Co., Ltd. | Electric device |
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