WO2001015252A1 - Materiau d'electrode positive pour accumulateur au lithium et electrode positive, et accumulateur au lithium - Google Patents

Materiau d'electrode positive pour accumulateur au lithium et electrode positive, et accumulateur au lithium Download PDF

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Publication number
WO2001015252A1
WO2001015252A1 PCT/JP2000/005338 JP0005338W WO0115252A1 WO 2001015252 A1 WO2001015252 A1 WO 2001015252A1 JP 0005338 W JP0005338 W JP 0005338W WO 0115252 A1 WO0115252 A1 WO 0115252A1
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lithium
composite oxide
manganese composite
positive electrode
lithium secondary
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PCT/JP2000/005338
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English (en)
Japanese (ja)
Inventor
Tsuyoshi Sueyoshi
Hidekazu Miyagi
Syouichirou Mori
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Mitsubishi Chemical Corporation
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Publication of WO2001015252A1 publication Critical patent/WO2001015252A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
    • C01G51/52—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(CoxMn2-x)O4, Li2(MyCoxMn2-x-y)O4
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/52—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(NixMn2-x)O4, Li2(MyNixMn2-x-y)O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a positive electrode material for a lithium secondary battery, a positive electrode for a lithium secondary battery, and a lithium secondary battery.
  • lithium manganese complex oxide complex oxides containing lithium and manganese as main components (hereinafter sometimes referred to as “lithium manganese complex oxide”) have large reserves of Mn compared to Co and Ni and are inexpensive. Because of that, it is attracting attention.
  • the lithium manganese composite oxide having a spinel crystal structure (L IMN 2 0 and 4), which describes the use of lithium-manganese composite oxide having a large capacitance layered structure of L IMN 2 0 4 than the unit weight equivalents have enough of a mixture of (L i Mn 0 2) as a positive electrode active material .
  • the Hei 9 one 306 475 discloses, in order to suppress the decrease in capacity by supplementing the L i incorporated irreversibly during initial charge, lithium-manganese composite oxide having a spinel crystal structure and (L iMn 2 0 4) L i 2 Mn 2 0 4 tetragonal lithium Umumangan composite oxide represented (hereinafter, referred to as tetragonal lithium-manganese composite oxide) Are described.
  • Japanese Patent Application Laid-Open No. H10-1499882 discloses a lithium manganese composite oxide having a subinel crystal structure (in order to solve the problem of trapping lithium ions in the negative electrode at the time of initial charging and to reduce cycle deterioration).
  • lithium manganese composite oxide having a spinel structure When a lithium manganese composite oxide having a spinel structure is used as a positive electrode active material, there is a problem that the capacity is greatly reduced due to charge / discharge cycles and storage under high temperature conditions. There is a problem. A similar problem occurs when a lithium manganese composite oxide having a layered structure is used as the positive electrode active material, because the active material undergoes repeated charge and discharge, whereby the transition to the Svinel structure proceeds.
  • tetragonal lithium-manganese composite oxide represented by L i 2 M n 2 0 4 is conventionally a Subineru type lithium manganese complex oxide, and reflux in Asetonitoriru solvent solution containing L i I prepared To produce a battery using spinel-type lithium manganese composite oxide as a positive electrode and Li metal as a negative electrode and electrochemically discharge it. not only known method such as to obtain a L i 2 M n 2 0 4 was refluxed at hexane solution, these methods were industrially disadvantageous production method.
  • An object of the present invention is to suppress the above-mentioned performance degradation at high temperatures (capacity reduction due to charge / discharge cycles and storage under high temperature conditions), and to provide a lithium secondary battery with excellent battery characteristics at high temperatures. It is to provide a material and a lithium secondary battery.
  • L i 2 Mn 2 0 4 with a compound in which a part of Mn sites tetragonal lithium-manganese composite oxide is substituted with another element other than L i found that as possible out, represented by (1) Subineru has a crystal structure, and lithium-manganese composite oxide in which a part of Mn sites is substituted with another element, (2) L i 2 Mn 2 0 4
  • the present inventors have also found that a combination of a tetragonal lithium manganese composite oxide and a compound in which a part of the Mn site is substituted with an element other than Li is industrially advantageous, and have completed the present invention.
  • (1) has a spinel crystal structure, and lithium-manganese composite oxide in which a part of Mn Sai Bok is substituted with another element, (2) L i 2 Mn 2 0 4 Of the tetragonal lithium manganese composite oxide represented by the formula (1), characterized in that it contains a compound in which part of the Mn site is substituted with an element other than Li and Z or a lithium manganese composite oxide having a layered structure.
  • the positive electrode material for lithium secondary batteries In the positive electrode material for lithium secondary batteries.
  • the second gist of the present invention is as follows: (1) a lithium manganese composite oxide having a spinel crystal structure and a part of Mn site substituted by another element; and (2) a lithium manganese composite oxide having a layered structure. And a positive electrode material for a lithium secondary battery.
  • the third aspect of the present invention (1) has a spinel crystal structure, and lithium-manganese composite oxide in which a part of Mn Sai I are substituted by other elements, by (2) L i 2 Mn 2 0 4
  • the positive electrode material for a lithium secondary battery is characterized in that a part of the Mn site of the represented tetragonal lithium manganese composite oxide contains a compound substituted with an element other than Li.
  • a fourth gist of the present invention is that the other element that substitutes for the Mn site of the lithium manganese composite oxide having a spinel crystal structure includes Al, Ti, V, Cr, Fe, Li, Co, Ni, Cu,
  • a lithium manganese composite oxide having a spinel crystal structure, wherein the other element that substitutes for the Mn site is a group consisting of Al, Cr, Fe, Li, Co, Ni, Mg, and Ga. 4.
  • the positive electrode material for a lithium secondary battery according to any one of the first to third aspects, wherein the positive electrode material is one or more other elements selected from the group consisting of:
  • a sixth gist of the present invention is that the other element that replaces the Mn site of the lithium manganese composite oxide having a spinel crystal structure is one or more other elements selected from the group consisting of Al, Li, and Mg.
  • the positive electrode material for a lithium secondary battery according to any one of the first to third aspects, characterized in that:
  • the lithium-manganese composite oxide having a subinel crystal structure, wherein the weighted average valence of another element that substitutes the Mn site is less than 3.5. O in the positive electrode material for lithium secondary batteries described in any one of (1) to (6)
  • the eighth gist of the present invention is characterized in that the substitution ratio of the lithium manganese composite oxide having a subinel crystal structure with another element of the Mn site is 1 to 30 mol% or less of Mn. 7.
  • a lithium manganese composite oxide having a layered structure, wherein a part of the Mn site is substituted with another element.
  • the positive electrode material for a lithium secondary battery according to the gist of the invention is provided.
  • the tenth gist of the present invention is that a part of the Mn site of the lithium manganese composite oxide having a layered structure includes Al, Ti, V, Cr, Fe, Li, Co, Ni, Cu, Zn , Mg, Ga, Zr, Nb, Mo, Pb, the gist of any one of the above first, second, fourth to eighth, characterized by being substituted with at least one other element selected from the group consisting of: To The positive electrode material for a lithium secondary battery described above.
  • the eleventh gist of the present invention is that part of the Mn site of the lithium manganese composite oxide having a layered structure is substituted by another element having a weighted average valence of less than 3.5.
  • another element substituting a part of Mn sites tetragonal lithium manganese composite oxide expressed by L i 2 Mn 2 0 4 is, Al, Ti, V, Cr , Fe, Li, Co, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Mo, and at least one other element selected from the group consisting of Pb, wherein
  • the weighted average valence of other elements substituting Mn site tetragonal lithium manganese composite oxide expressed by L i 2 Mn 2 0 4 is 3. less than 5
  • (1) has a spinel crystal structure, and lithium-manganese composite oxide in which a part of Mn sites is substituted with another element, with (2) L i 2 Mn 2 0 4
  • the weight ratio of the tetragonal lithium manganese composite oxide expressed to a compound in which a part of the Mn site is substituted by an element other than Li and / or a lithium manganese composite oxide having a layered structure is expressed by weight.
  • the positive electrode material for a lithium secondary battery according to any one of the first to thirteenth aspects, wherein the positive electrode material has a ratio of 10:90 to 98: 2.
  • Subineru has a crystal structure, and lithium-manganese composite oxide in which a part of Mn Sai I are substituted by other elements, by (2) L i 2 Mn 2 0 4
  • the weight ratio of the tetragonal lithium manganese composite oxide expressed to a compound in which a part of the Mn site is substituted by an element other than Li and / or a lithium manganese composite oxide having a layered structure is expressed by weight.
  • the positive electrode material for a lithium secondary battery according to any one of the first to fourteenth aspects, wherein the ratio is 50:50 to 95: 5 in a ratio.
  • a sixteenth aspect of the present invention resides in a positive electrode for a lithium secondary battery containing the positive electrode material for a lithium secondary battery according to any one of the first to fifteenth aspects as an active material.
  • a seventeenth aspect of the present invention is directed to a lithium secondary battery positive electrode comprising the lithium secondary battery positive electrode material according to any one of the first to the fifteenth aspects as an active material, comprising a carbon material as an active material.
  • a lithium secondary battery comprising a negative electrode and an electrolyte layer.
  • An eighteenth aspect of the present invention resides in a tetragonal lithium manganese composite oxide in which a part of Mn site is replaced by an element other than Li.
  • a nineteenth aspect of the present invention is that the other element is selected from the group consisting of Al, Ti, V, Cr, Fe, Li, Co, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Mo, and Pb.
  • the tetragonal lithium manganese composite oxide according to the eighteenth aspect characterized in that it is one or more other elements selected.
  • a twentieth aspect of the present invention resides in a positive electrode for a lithium secondary battery containing the tetragonal lithium manganese composite oxide described in the eighteenth or nineteenth aspect as an active material.
  • a twenty-first aspect of the present invention is a positive electrode for a lithium secondary battery containing the tetragonal lithium manganese composite oxide according to the eighteenth or nineteenth aspect as an active material, a negative electrode containing a carbon material as an active material, And a lithium secondary battery comprising an electrolyte layer.
  • the lithium manganese composite oxide in the present invention is a composite oxide containing lithium and manganese as main components.
  • Lithium-manganese composite oxide having a spinel crystal structure is represented by L iMn 2 0 4
  • the lithium manganese composite oxide having a layered structure is represented by iMn0 2
  • tetragonal lithium manganese composite oxide L i 2 Mn 2 0 represented by 4
  • a small amount of oxygen deficiency may have a nonstoichiometric.
  • the lithium manganese composite oxide (lithium-manganese complex oxide having a spinel crystal structure, the lithium manganese composite oxide having a layered structure, tetragonal lithium represented by L i 2 Mn 2 0 4 Part of Mn site of manganese composite oxide is other than Li Compounds substituted with other elements) are used as active materials.
  • the active material is a main substance that causes an electromotive reaction of the battery, and means a substance capable of inserting and extracting Li ions.
  • lithium manganese composite oxide having a spinel crystal structure requires that a part of Mn site is replaced by another element. I do.
  • the other element that replaces the Mn site hereinafter, referred to as a substitution element
  • Al, Ti, V, Cr, Fe, Li, Co, Ni, Cu, and Zn , Mg, Ga, Zr, etc. preferably Al, Cr, Fe, Co, Li, Ni, Mg, Ga, and particularly preferably Al, Li, Mg.
  • the Mn site may be substituted with two or more other elements, and when substituted with Li, it is preferable that the Mn site is further substituted with another element other than Li.
  • the substitution element preferably has an average valence calculated by a weighted average taking into account the composition (hereinafter, referred to as a weighted average valence) of less than 3.5 for the Svinel-type lithium manganese composite oxide. If the average valence is too large, the crystal structure is significantly degraded due to charge and discharge, and the problem that Mn elution at high temperatures proceeds easily occurs.
  • the average valence is calculated by the following equation.
  • tetragonal lithium manganese double if oxide represented by L i 2 Mn 2 0 4 in the present invention essentially includes a part of the Mn site I is substituted with another element other than L i,
  • a part of Mn site may be substituted with another element.
  • L i 2 Mn 2 0 compounds substituted portion of Mn sites tetragonal lithium-manganese composite oxide represented by 4 with another element other than L i by industrially advantageous method for discussed later It can be produced and is more advantageous than unsubstituted tetragonal lithium manganese composite oxide.
  • the weighted average valence of the substitution element is preferably less than 3.5.
  • substitution element include metal elements such as Al, Ti, V, Cr, Fe, Li, Co, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Mo, and Pb, and preferably Al, Cr, Fe , Li, Co, Ni, Mg, and Ga, and particularly preferably Al, Cr, Fe, Li, Co, and Ni.
  • the Mn site may be substituted with two or more other elements, and when the lithium manganese composite oxide having a layered structure is substituted with Li, it may be further substituted with another element other than Li. Substituted ones are preferred, and in the case of tetragonal lithium manganese composite oxides, those substituted with elements other than Li and Li are preferred.
  • lithium manganese composite oxide having a spinel crystal structure is represented by i 2 Mn 2 0 4 It may be the same or different from the other element that partially replaces the Mn site of the tetragonal lithium manganese composite oxide.
  • the substitution ratio of the lithium manganese composite oxide having a subinel crystal structure by a substitution element is usually 30 mol% or less of Mn, preferably 20 mol% or less, and usually 1 mol% or more, preferably 3 mol% or more. is there. If the substitution ratio is too small, the effect of improving the high-temperature cycle may not be sufficient, and if it is too large, the capacity of the battery may decrease.
  • the substitution ratio by the substitution element is usually 70 mol% or less of Mn, preferably 60 mol% or less, more preferably 30 mol% or less. If the replacement ratio is too large, the capacity of the battery may decrease.
  • Substituted proportion by substituting element in the case of tetragonal lithium manganese composite oxide expressed by L i 2 Mn 2 0 4, and 30 mol% or less of the normal Mn, is preferably 20 mol% or less, usually It is at least 1 mol%, preferably at least 3 mol%. If the substitution ratio is too small, the effect of improving the high-temperature cycle may not be sufficient, and if it is too large, the capacity of the battery may decrease.
  • the lithium manganese composite oxide having a spinel crystal structure, lithium-manganese composite oxide have a layered structure, tetragonal Richiumuma represented by L i 2 Mn 2 0 4
  • a part of the oxygen site may be replaced by sulfur or a halogen element. Further, there may be some non-stoichiometric oxygen content.
  • the positive electrode material for a lithium secondary battery of the present invention is used as an active material of a positive electrode.
  • a lithium manganese composite oxide having a spinel crystal structure and a part of Mn site substituted with another element, the (2) L i 2 Mn 2 0 compound portion of Mn sites is substituted by another element other than L i tetragonal lithium manganese composite oxide expressed by 4 and / or layered structure
  • the compounding ratio with the lithium manganese composite oxide is 10:90 to 98: 2, preferably 20:80 to 97: 3, more preferably 30:70 to 95: 5, most preferably 50:50 by weight. ⁇ 95: 5.
  • the total amount of (1) and (2) is the main component, but other components may be contained.
  • the spinel-type lithium-manganese composite oxide in which a part of the Mn site is substituted by another element can be produced by various conventionally known methods. For example, lithium, manganese, a starting material containing the substitution element , And then calcined and cooled in the presence of oxygen.
  • lithium compound used as a starting material L i 2 C0 3, L iN0 3, L iOH, L i OH * H 2 0, L i C l, L il, CH 3 C00L i, L i 2 0, dicarboxylic acid L i, fatty acid L i, alkyllithium or the like.
  • the manganese compound used as a starting material Mn 2 0 3, Mn0 manganese oxides such as 2, MnC0 3, Mn (N0 3) 2, the dicarboxylic acid manganese salts, manganese salts such as fatty acid manganese, Okishi hydroxide And the like.
  • Mn 2 0 3 it may be used those prepared by heat-treating compound, such as MnC 0 3 and Mn0 2.
  • Examples of the compound of the substitution element include an oxide, a hydroxide, a nitrate, a carbonate, a dicarbonate, a fatty acid salt, and an ammonium salt.
  • a pulverizing step may be added before, after and during mixing.
  • a method of firing and cooling the spinel-type lithium manganese composite oxide for example, after calcination, main firing is performed in an oxygen atmosphere at a temperature of about 600 to 900 ° C, and then 1 O ⁇ Zmi
  • the method of slow cooling at a speed of n or less, or the method of calcining after calcining at about 600 to 900 ° C in air or oxygen atmosphere, and then annealing at about 400 ° C in oxygen atmosphere be able to.
  • the conditions for firing and cooling the conditions described in US Pat. No. 5,866,279, column 3 L54 to column 4 L21 (provided that column “600 to 850 ° 0” in column 362 is “600 to 850 ° 0” in the present invention) 900 ° C ”).
  • the specific surface area of the spinel-type lithium manganese composite oxide used in the present invention is usually at least 0.0 lm 2 / g, preferably at least 0.3 m 2 / g, more preferably at least 0.5 m 2 / g, It is usually at most 10 m 2 / g, preferably at most 1.5 m 2 Zg, more preferably at most 1.0 m 2 / g. If the specific surface area is too small, the rate characteristics will decrease and the capacity will decrease. If the specific surface area is too large, an undesirable reaction with the electrolyte or the like will be caused, and the cycle characteristics may deteriorate. The measurement of the specific surface area follows the BET method.
  • the average particle size of the lithium transition metal oxide used in the present invention is usually at least 0.1 m, preferably at least 0.2 ⁇ m, more preferably at least 0.3 ⁇ m, most preferably at least 0.5 m. Yes, usually 300 // m or less, preferably 100 m or less, moreover It is preferably 5 O ⁇ m or less, most preferably 2 O zm or less. If the average particle size is too small, the cycle deterioration of the battery may increase or safety problems may occur.If the average particle size is too large, the internal resistance of the battery may increase and output may become difficult. is there.
  • the lithium manganese composite oxide having a layered structure belonging to a hexagonal system, an orthorhombic system, or a monoclinic system can also be produced by various conventionally known methods.
  • the hexagonal lithium manganese composite oxide can be obtained, for example, by reacting an MnOOH with an aqueous solution of LiOH by a hydrothermal method.
  • a reaction condition there is a report of 150 days at 300 atmospheres for 5 days.
  • Orthorhombic lithium-manganese composite oxide for example, that after beating mixed ⁇ over MnOOH and L i OH and H 2 0, 100 was pressed into pellets of linch in OBAR, wrapped with N i foil A r It can be obtained by baking at 300-450 ° C under circulation. (J. Electrochem. So 149, 3396 (1993))
  • a monoclinic lithium manganese composite oxide can be synthesized, for example, by synthesizing NaMnO 2 and ion-exchange thereof (Nature 381, 499 (1996)).
  • N aMn0 2 can be obtained by a solid phase reaction of Na 2 C0 3 and Mn 2 0 3 (700-730.C 18-72 hr under Ar flow), key Sanol ion exchange to n- of L i B r It can be performed by refluxing in a solution.
  • Lithium-manganese composite oxides that belong to hexagonal, orthorhombic, or monoclinic systems and have a layered structure, and in which part of the Mn site is replaced with another element, are manufactured by various conventionally known methods. For example, after mixing starting materials containing lithium, manganese, and other elements (substituting elements), they can be manufactured by baking and cooling in an inert gas atmosphere, and can be manufactured under hydrothermal conditions. You can also. It can also be manufactured by firing and cooling under the flow of a reducing gas and in the presence of a reducing agent. It can also be produced by heating an organic solvent containing a spinel-type lithium manganese composite oxide and an alkyl lithium.
  • lithium manganese composite oxides that belong to hexagonal, orthorhombic, or monoclinic systems and have a layered structure, in which a part of the Mn site is replaced by another element, a part of the Mn site is other It can also be manufactured by firing a manganese oxide substituted with an element and a lithium compound.
  • Manganese oxide part of the Mn site de was replaced with other elements as the raw material, the compound valence of Mn is trivalent are preferred, as the manganese oxide, for example, Mn 2 0 3 and The Amer i CAN Meneral ogi st Vo l. 50 ( 1 965) can be exemplified ⁇ one Mn 2 0 3 described on pages 1296. Although a small amount of water may be added to these compounds, it is preferable that the amount of the added compound is small because a large amount of the compound reduces the yield after firing.
  • the other element is at least one metal selected from Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Mg, Ga, Zr, Nb, Mo and Pd.
  • Element and preferably, Al, V, Cr, Fe, Co, Ni, Mg, Cu, and Zn.
  • Such a manganese oxide in which other elements are uniformly distributed can be produced, for example, by performing the following steps (1) to (3). These steps may be performed separately from each other, or may be performed partially.
  • Step (2) A step of forming a coprecipitated compound by increasing the OH concentration of the solution or suspension generated in Step (2),
  • At least one compound containing Mn and at least one other elemental compound in step (1) are not particularly limited, but inorganic acid salts such as nitrates and sulfates, organic acid salts such as acetates and oxalates, and carbonates Salts, ammonium salts, oxides and the like. These compounds may be used as they are, or may be used in the form of a sol. other
  • the ratio of the number of moles of the element to the sum of the number of moles of Mn and the number of moles of the other element (substituting element) is from 0.005 to 0.5, preferably from 0.01 to 0.4.
  • the total concentration of Mn and other elements (substitution elements) in the solution or suspension is 0.01 to 10 mol / l, preferably 0.02 to 5 mol / l.
  • the liquid temperature There is no particular limitation on the liquid temperature, and the temperature may be changed on the way.
  • the method of increasing the OH_ concentration of the solution or suspension generated in the step (2) is not particularly limited, and examples thereof include a method of adding an alkali metal hydroxide, an aqueous solution thereof, and ammonia water.
  • the alkali metal hydroxide include sodium hydroxide and lithium hydroxide.
  • Oxidants such as hydrogen peroxide and oxygen may be added before, during, or after increasing the OH concentration.
  • the temperature of the solution is not particularly limited, but an appropriate temperature can be selected when the oxidizing agent is added, and the solution may be heated to control the particle properties of the coprecipitated compound formed by the precipitation.
  • the heating temperature is appropriately selected usually in the range of 100 ° C. or lower, preferably 90 ° C. or lower, and usually in the range of 30 ° C. or higher. In this step, it is desirable to stir the solution or suspension.
  • step (3) conventionally known various methods can be used for separating the coprecipitated compound formed in the step (2), for example, centrifugal filtration, reduced pressure filtration, centrifugation, decantation, and the like.
  • it is desirable to wash the cake after separation after separation and it is desirable to control the pH of the washing solution so that the cake is not eluted.
  • the drying and baking of the cake may be performed independently, but the drying may be performed continuously as part of the baking operation, or only the baking may be performed.
  • Examples of a method for drying the coprecipitated compound include a method in which the compound is heated in air at 30 to 200 ° C. for 2 to 24 hours.
  • the calcination temperature is 200 to 1200 ° C, preferably 350 to 110 ° C, and more preferably 450 to 1000 ° C. Outside of the above range, it is difficult to adjust the Mn valence to trivalent.
  • the firing time is preferably from 1 hour to 50 hours. Below the above range, the effect of firing is not sufficiently exhibited, and above the above range, it is difficult to recognize a difference in the effect of firing. No.
  • the firing atmosphere is desirably under an oxygen-containing gas, for example, under air. A gas containing oxygen may be circulated. Drying and baking may be performed in a continuous manner or in a patch manner.
  • the Mn compound and the other element compound may be dry-mixed and crushed, and then calcined in the presence of oxygen. Firing can be performed under the same conditions as in step (3) above.
  • a manganese oxide or a hydrate thereof in which a part of the Mn site obtained by the above-mentioned production method is substituted with another element is mixed with a lithium compound.
  • a lithium compound By firing under an inert gas, it is possible to produce a lithium manganese composite oxide having a layered structure.
  • lithium compound Li 2 C0 3, L iN0 3, inorganic acid salts and the like, L IOH, hydroxides such as L i OH ⁇ H 2 0, L i C l, halides such as L i I, Li oxides of 2 0, etc., CH 3 COOLi, dicarboxylic acids L i, organic acid salts such as fatty acid L i, alkyl lithium such as petit butyllithium and the like.
  • a conventional mixing method As a method of mixing the manganese oxide and the lithium compound, a conventional mixing method is used, and examples thereof include wet mixing and spray drying, dry mixing, and ball mill pulverization.
  • the mixture of the manganese oxide and the lithium compound is calcined under an inert gas.
  • the inert gas at that time include nitrogen, argon, and helium.
  • the firing temperature is from 350 ° C to 1200 ° C, preferably from 500 ° C to 1000 ° C. Below the above range, Li does not diffuse sufficiently, and above the above range, Li may volatilize, and both are not preferred.
  • the firing time is from 1 hour to 72 hours, preferably from 2 hours to 50 hours. Below the above range, the effect of firing cannot be sufficiently obtained, and it is difficult to recognize a difference in effect even if firing is performed for a long time beyond this range.
  • lithium manganese composite oxides having various crystal structures such as a spinel type can be generated, but the target here is a lithium manganese composite oxide having a layered structure. It is.
  • a manganese oxide in which part of the Mn site is replaced with another element as the manganese compound an easy operation method of mixing and firing each component compound of lithium and manganese, and appropriately selecting the firing conditions
  • a lithium manganese composite oxide having a layered crystal structure can be appropriately and selectively manufactured. For example, manufacturing a layered lithium manganese composite oxide by reducing the oxygen concentration during firing to 10,000 ppm or less, preferably 100 ppm or less, or by changing the firing in air to a reducing atmosphere. Can be.
  • the particle size of the primary particles of the lithium manganese composite oxide having a layered structure obtained by the above method is from 0.01 m to 50 / zm, preferably from 0.02 Aim to 30 m.
  • the particle size is smaller than the above range, a side reaction with the electrolyte may be induced when used as a positive electrode active material of a lithium secondary battery.
  • L i between the active material and the electrolyte may be reduced. It is not preferable because diffusion is hindered and a problem may occur in use at a high current density.
  • the particle size of the secondary particles 0.
  • the specific surface area is from 0.05 m 2 Zg to 100 m 2 / g, preferably from 0.1 m 2 / g to 50 m 2 / g. If it is less than the above range, the diffusion of L i between the active material and the electrolyte is inhibited, and if it is larger than the above range, a side reaction with the electrolyte may be induced.
  • a tetragonal lithium manganese composite oxide in which part of the Mn site has been replaced by an element other than Li must be manufactured by a method of mixing and sintering the Mn compound, lithium compound, and other metal element compounds. Can be.
  • Other production methods include manganese oxide in which part of the Mn site is replaced with another element, or manganese hydroxide manganese in which part of the Mn site and / or H site is replaced with another element.
  • a method comprising mixing and sintering with a lithium compound can also be employed.
  • the compound of the other element is not particularly limited, and various oxides, hydroxides, inorganic salts, carbonates, organic acid salts, and ammonium salts can be used as appropriate.
  • carbonates, Oxides and hydroxides are preferred, and manganese oxide in which a part of the Mn site is replaced with another element, or an oxide in which a part of the Mn site and / or H site is replaced with another element.
  • solvents such as inorganic acid salts such as nitrates and sulfates and organic acid salts such as oxalate salts, which are suitable for preparing these oxides and oxyhydroxide manganese, are used. Soluble salts are preferred.
  • lithium compound examples include L i 2 C0 3, L iN0 3, inorganic acid salts and the like, L IOH, hydroxides such as L i OH ⁇ H 2 0, L iCl, halides such as L i I, L i oxides of 2 0, etc., CH 3 COOL i, dicarboxylic acids L i, organic acid salts such as fatty acid L i, alkyl lithium such as petit butyllithium and the like.
  • manganese oxide or manganese oxyhydroxide can be used as the Mn compound.
  • the manganese oxide is preferably a compound valence of Mn is trivalent, e.g. Mn 2 0 3 and The Ame ri can Meneral ogi st V o 1. 50 (1965) ⁇ over Mn 2 0 described on pages 1296 3 can be mentioned. Although a small amount of water may be added to these compounds, it is preferable that the amount of the added compound is small because a large amount of the compound decreases the yield after firing.
  • a manganese oxide in which a part of the Mn site is substituted by the above-mentioned other element can be used as the manganese oxide.
  • manganese hydroxide those in which the Mn site and the Z or H site are substituted with the above-mentioned other elements can also be used.
  • manganese oxides or manganese oxyhydroxides substituted with other elements those substituted with a plurality of other elements can be used.
  • Sintering may be carried out in the presence of a manganese oxide or lithium compound substituted with another element and a compound containing another kind of another element.
  • a manganese oxide in which a part of the Mn site is substituted by another element it is desirable that the other element be uniformly distributed in the oxide.
  • Such a manganese oxide in which other elements are uniformly distributed can be produced, for example, by performing the following steps (1) to (3). These steps may be performed separately from each other, or may be performed partially. (1) dissolving or suspending at least one compound containing Mn and at least one other element compound in water, an organic solvent, or a mixture thereof;
  • step (1) a step of forming a coprecipitated compound by increasing the OH concentration of the solution or suspension produced in step (1)
  • At least one compound containing Mn and at least one other element compound in the above step (1) are not particularly limited, but may be inorganic salts such as nitrates and sulfates, and acetates and oxalates. Organic salts, carbonates, ammonium salts, oxides and the like can be mentioned. These compounds may be used as they are, or may be used in the form of a sol.
  • the ratio of the mole number of the other element to the sum of the mole number of Mn and the mole number of the other element is 0.005 or more and 0.5 or less, and preferably 0.01 or more and 0.4 or less.
  • the total concentration of Mn and other elements in the solution or suspension is 0.01 to 10 mol / 1, preferably 0.02 to 5 mol 1Z1.
  • the liquid temperature There is no particular limitation on the liquid temperature, and the temperature may be changed on the way.
  • the hydroxide of alkali metal and its aqueous solution and aqueous ammonia are used.
  • the alkali metal hydroxide include sodium hydroxide and lithium hydroxide.
  • An oxidizing agent such as hydrogen peroxide or oxygen may be added before, during, or after increasing the OH_ concentration.
  • the temperature of the solution is not particularly limited, but an appropriate temperature can be selected when the oxidizing agent is added, and the solution may be heated to control the particle properties of the coprecipitated compound formed by the precipitation.
  • the heating temperature is appropriately selected usually in the range of 100 ° C or lower, preferably 90 ° C or lower, and usually in the range of 30 ° C or higher. In this step, it is desirable to stir the solution or suspension.
  • step (3) conventionally known various methods can be used for separating the coprecipitated compound generated in the step (2), and examples thereof include centrifugal filtration, vacuum filtration, centrifugal separation, and decantation. .
  • the resulting cake is subsequently washed. It is desirable to control the pH of the washing solution so that the cake is not eluted.
  • the drying and baking of the cake may be performed independently, but may be performed continuously, in which case the drying may be performed as part of the baking operation.
  • a method of drying the coprecipitated compound for example, a method of heating at 30 to 200 ° C. for 2 to 24 hours under air may be mentioned.
  • the firing temperature is from 200 to 1200 ° C., preferably from 350 to 110 ° C., and more preferably from 450 to 100 ° C. Outside the above range, it is difficult to adjust the M n valence to trivalent.
  • the firing time is preferably 1 hour or more and 50 hours or less. Below this range, the effect of sintering is not sufficiently exhibited, and even if it is baked above this range, it is difficult to recognize a significant difference in the effect.
  • the firing atmosphere is desirably under an oxygen-containing gas, for example, under air. A gas containing oxygen may be passed. Drying and firing may be performed in a continuous manner or in a batch manner.
  • Another method for producing a manganese oxide in which a part of the Mn site is replaced by another element is to dryly mix and crush the Mn compound and the other element compound, and then calcinate in the presence of oxygen. good.
  • the firing can be performed under the same conditions as in the above step (3).
  • a conventional mixing method is used as a method for mixing the Mn compound, the lithium compound, and the other element compound. Examples thereof include wet mixing and spray drying, dry mixing, ball milling, and the like.
  • firing in an inert gas atmosphere can be mentioned.
  • the inert gas include nitrogen, argon, and helium.
  • the firing temperature is 350 ° C. or more and 1200 ° C. or less, preferably 500 ° C. or more and 100 ° C. or less. Below the above range, Li does not diffuse sufficiently, and above the above range, Li may volatilize, which is not preferable.
  • the firing time is from 1 hour to 72 hours, preferably from 2 hours to 50 hours. Below the above range, the effect of firing cannot be sufficiently obtained, and it is difficult to recognize a difference in effect even if firing is performed for a long time beyond this range.
  • Lithium-manganese composite oxides of various crystal structures such as types can be produced, but it has been considered difficult to produce tetragonal lithium-manganese composite oxides.
  • a tetragonal lithium manganese composite oxide can be obtained by an easy operation method of mixing and firing each of the above component compounds. .
  • the tetragonal lithium manganese composite oxide in which a part of the Mn site is substituted by another element can be appropriately and selectively produced by appropriately selecting the firing conditions.
  • it can be produced by reducing the oxygen concentration during firing to 10,000 ppm or less, preferably 1000 ppm or less, or by changing the firing in air to a reducing atmosphere.
  • the particle size of the primary particles of the tetragonal lithium manganese composite oxide is 0.0 or more and 5 or less, preferably 0.02 zm or more. It is as follows. If the particle size is too small, when used as a positive electrode active material of a lithium secondary battery, a side reaction with the electrolyte may be induced.If the particle size is too large, diffusion of Li between the active material and the electrolyte may be inhibited. However, it is not preferable because a problem may occur in use at a high current density. There is no particular limitation on the shape of the primary particles.
  • the particle size of the secondary particles is 0.1 Aim or more and 100 m or less, preferably 0.1 or more and 6 or less.
  • the specific surface area is 0. 05m 2 / g or more 100 m 2 / g or less, rather preferably is less 0. lm 2 / g or more 50 m 2 / g. If it is less than the above range, diffusion of Li between the active material and the electrolyte may be inhibited, and if it is larger than the above range, a side reaction with the electrolyte may be induced.
  • the positive electrode material for a lithium secondary battery of the present invention is used as an active material of a positive electrode of a lithium secondary battery, and such a positive electrode usually contains the above active material, a binder, and a conductive agent.
  • the binding agent include polyvinylidene fluoride, polytetrafluoroethylene, EPDM (ethylene-propylene-diene terpolymer), SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), Fluorine rubber and the like can be mentioned.
  • the conductive agent graphite fine particles, acetyl Examples include carbon black such as len black, and amorphous carbon fine particles such as needle coke.
  • the contents of the active material, the binder and the conductive agent in the positive electrode are usually about 20 to 90% by weight, about 10 to 50% by weight, and about 1 to 20% by weight, respectively.
  • the positive electrode can be obtained by applying and drying a slurry containing the above materials.
  • the positive electrode is a lithium secondary battery in combination with the negative electrode and the electrolyte layer.
  • any of the materials usually used for this type of lithium secondary battery can be used.
  • a carbon-based material that is favorably used as a negative electrode agent for a lithium ion battery can be used.
  • Lithium alloys such as lithium metal, Al, Si, Sn, Pb, In, Bi, Sb, and Ag, and lithium at a relatively low potential of 2 V or less with respect to Li metal. reversibly de one flop, dedoping possible M o 0 2, W 0 2 , T i S 2, T i 0 2 transition metal oxide is have the sulfides such as news or amorphous tin composite oxide Richiumu A nitride or the like can be used.
  • the carbon-based material natural graphite, artificial graphite, coal-based and petroleum-based coke pitches, resin compositions such as phenol resin, and carbonized various celluloses at a high temperature may be used. it can. Further, a composite of two or more of these carbon-based materials, or a composite of two or more of the above-described non-carbon-based materials and carbon-based materials can also be used.
  • the use of the above-mentioned negative electrode active material is not particularly limited.Natural graphite materials, artificial graphite materials, and amorphous carbon materials made from pitch coke alone or in combination are generally used. Have been.
  • the negative electrode usually contains the above active material and a binder.
  • the binder the same material as that for the positive electrode can be used.
  • the same method as that for the positive electrode can be used for the production.
  • the electrolyte layer is usually composed of an ion conductor made of an electrolyte and a separator.
  • a separator When using a separator, a microporous polymer film is usually used, and nylon, cellulose acetate, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, and polybutane Those made of polyolefin polymers such as ten are used.
  • the chemical and electrochemical stability of Separet is an important factor.
  • polyolefin polymers are preferred, and it is desirable that the battery be made of polyethylene from the viewpoint of the self-closing temperature, which is one of the purposes of battery separation.
  • the polyethylene separator it is preferably ultra-high molecular weight polyethylene from the viewpoint of high-temperature shape retention, and the lower limit of the molecular weight is preferably 500,000, more preferably 100,000, and most preferably 150,000.
  • the upper limit of the molecular weight is preferably 500,000, more preferably 400,000, and most preferably 300,000. If the molecular weight is too small, the blocking property becomes too high, causing problems in use at high temperatures.If the molecular weight is too large, the flowability is too low, so that the pores in the separator do not block when heated. There is.
  • the ion conductor in the lithium secondary battery of the present invention for example, a known organic electrolyte, a polymer solid electrolyte, a gel electrolyte, an inorganic solid electrolyte, or the like can be used, and among them, an organic electrolyte is preferable.
  • the organic electrolyte is composed of an organic solvent and a solute.
  • the organic solvent is not particularly restricted but includes, for example, carbonates, ethers, ketones, sulfolane compounds, lactones, nitriles, chlorinated hydrocarbons, ethers, amines, esters , Amides, phosphate compounds and the like can be used.
  • Typical of these are propylene carbonate, ethylene carbonate, vinylene carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 4-methyl-2-benzenone, 1,2-dimethoxetane, 1 , 2—Jetokishetan, Arptiloractone, 1,3-Dioxolane, 4-Methyl-1,3-Dioxolane, Jethyleether, Sulfolane, Methylsulfolane, Acetonitrile, Propionitryl, Benzonitrile, Butyronitrile, Norel, 1, Reloni -A single solvent or a mixture of two or more solvents such as dichloroethane, dimethylformamide, dimethylsulfoxide, trimethyl phosphate and triethyl phosphate can be used.
  • solvents such as dichloroethane, dimethylformamide, dimethylsulfoxide, trimethyl phosphat
  • the solute to be dissolved in this solvent is not particularly limited. Any of the known can be used, L i C10 4, L iAsF 6, L i PF 6, L i BF 4, LiB (C 6 H 5) 4, LiCl, L iBr, CH 3 S0 3 L i, CF 3 S0 3 L i, etc. lithium salts may be mentioned of, as possible out be those of at least one or more of these.
  • a known polymer can be used as the polymer.
  • a polymer having high ionic conductivity to lithium ions is preferably used.
  • polyethylene oxide and polypropylene are used.
  • Oxide, polyethylenimine and the like are preferably used, and the polymer can be used as a gel electrolyte by adding the above solvent together with the above solute.
  • La, Pr include at least one), such as selected from the group consisting of Nd and Sm, as the solid electrolyte of the amorphous example, 4.9 L i I one 34.1L i 2 0- 61 B 2 0 5, 33.3 Oxide glass such as L 2 0—66.7S i 0 2 or 0.45L i I -0.37L i 2 S—0.26B 2 S 3 , 0.30 L i I -0.42 L i 2 S—0.28S i S 2 Sulfide glass and the like. At least one or more of these can be used.
  • tetragonal lithium manganese composite oxide in which part of the Mn site is replaced by another element is a novel compound, and this compound is useful for improving the high-temperature characteristics of lithium manganese oxide having a svinel crystal structure.
  • the details of the tetragonal lithium manganese composite oxide in which a part of the Mn site is substituted by another element are as described above, and the tetragonal lithium manganese composite oxide in which a part of the Mn site is substituted by another element.
  • An oxide is also one of the present invention.
  • the high-temperature cycle characteristics were evaluated by a charge / discharge cycle test in which the charge / discharge current density was 1 mA / cm 2 and the voltage range was 4.2 V to 3.0 V and the constant current charge / discharge was performed.
  • the capacity retention rate was calculated by the following formula.
  • Lithium hydroxide monohydrate (L i OH ⁇ ⁇ 2 0 ), ⁇ oxide manganic (Mn 2 0 3), Bemai preparative (A100H), L i, Mn , each molar ratio of A 1 (L i: Mn: A1) was weighed in such an amount that it became 1.03: 1.85: 0.12, mixed well, and fired at 880 ° C for 24 hours.
  • the result of powder XRD was compared with that of JC PDS card 35-0782, and as a result, it was confirmed that the powder was a lithium manganese composite oxide having a subinel crystal structure.
  • Lithium-manganese composite oxide Li having a layered structure in which Mn sites are substituted with Cr. 5 Mn 0. 9 Cr 0 ⁇ manufacturing
  • the positive electrode active material a mixture of the lithium manganese composite oxide having a spinel crystal structure manufactured in the above (1) and the lithium manganese composite oxide having a layered structure manufactured in the above (2) in a weight ratio of 3: 1.
  • Acetylene black is used as the conductive agent, and polytetrafluoroethylene resin is used as the binder.
  • the positive electrode active material: conductive agent: binder is mixed at a weight ratio of 75: 20: 5. Made the material. Next, the positive electrode mixture was formed into a sheet to obtain a positive electrode.
  • Graphite and polyvinylidene fluoride (PVdF) as a binder were used in a weight ratio of 90:10 to form a paste using N-methylbipyridine as a solvent.
  • the coated negative electrode was coated on one side, dried and evaporated to form a negative electrode by pressing at a pressure of 0.5 t / cm 2 , and the obtained coated negative electrode was punched out to a diameter of 12 mm.
  • a battery was prepared using the above positive electrode and negative electrode.
  • a porous polypropylene film was placed on the positive electrode as a separator, and the negative electrode (12 mm in diameter and 0.5 mm in thickness of lithium foil) was pressed on a sealed can with a polypropylene gasket. I wore it.
  • Non-aqueous electrolyte as 1 mol / 1 of L i PF 6 the dissolved ethylene carbonate ne one preparative and Jechiruka - BONNET - mixing of the bets solution (50vo l%: 50 V o 1%) using a separator of this Added in the evening and on the negative electrode. Thereafter, the battery was sealed to form a lithium secondary battery (potan type).
  • Example 2 Example 2
  • LiMnO 2 lithium manganese composite oxide having a layered structure in which the Mn site is not substituted with other elements
  • Lithium hydroxide monohydrate (. L iOH H 2 0) , the Okishi manganese hydroxide (MnO OH), L i, the molar ratio of Mn (Li: Mn) is 1.05: 2.00 and so as
  • the mixture was weighed in an appropriate amount, mixed well, and calcined at 900 ° C for 10 hours under a nitrogen flow.
  • a comparison of the powder XRD with JCPDS card 35-0749 revealed that the powder was a layered lithium-manganese composite oxide belonging to orthorhombic.
  • Example 1 instead of the lithium manganese composite oxide (L i L Q5Mno. 9Cro. IO2) having a layered structure in which the Mn site obtained in (2) of Example 1 was substituted with Cr, the above was obtained.
  • a battery was prepared in the same manner as in Example 1 except that a lithium manganese composite oxide having a layered structure in which the Mn site was not substituted with another element was used. Comparative Example 1
  • Lithium hydroxide monohydrate (L i OH ⁇ H 2 0 ), the manganese sesquioxide (Mn 2 0 3), L i, each the molar ratio of Mn (L i: Mn) is 1.04: 1.
  • the mixture was weighed to an amount of 96, mixed well, and baked at 800 ° C for 24 hours.
  • lithium manganese composite oxide LiMn 85Alo.i2Lio.03O4
  • the Mn site obtained in Example 1 (2) was a Cr-based Mn site obtained in Example 1 (2)
  • lithium manganese composite oxide having a Svinel crystal structure in which the Mn site obtained above was not substituted with another element.
  • lithium-manganese composite oxide having a substituted layered structure Li i !. 05 Mn 0.
  • a battery was prepared in the same manner as in Example 1, except that a lithium manganese composite oxide having a layered structure (LiM nO 2 ) was used. Comparative Example 2 Only the lithium manganese composite oxide (LiMnL85Alo.i2Lio.03O4) having a Svinel crystal structure in which the Mn site obtained in (1) of Example 1 was substituted with A1 was used as the positive electrode.
  • Example 2 The same procedure as in Example 1 was carried out except that only the lithium manganese composite oxide having a Svinel crystal structure in which the Mn site obtained in (1) of Comparative Example 1 was not substituted with another element was used as the positive electrode active material. Battery was created.
  • Cathode material (1) Cathode material (2) Cycle maintenance rate Example 1 With spinel substitution Layered substitution 94%
  • Comparative Example 1 is a combination known in JP-A-8-7883 and the like, but Examples 1 and 2 have a remarkable effect as compared with Comparative Example 1. This is part of the Mn site This is due to a synergistic effect of a combination of a lithium manganese composite oxide having a spinel crystal structure substituted with another element and a lithium manganese composite oxide having a layered structure. In fact, lithium manganese composite oxide with spinel crystal structure
  • lithium manganese composite oxide LiL05Mno.9Cro.iO2
  • Mn Sai we have created a manner batteries same manner as in example 1 except for using tetragonal lithium-manganese composite oxide which is substituted with N i a (L i 2 osMn !. 76 N i 2 Q0 4) were .
  • the positive electrode material (1) cathode material (2) Cycle retention rate
  • Example 3 LiMn 185 Al 012 Li 0. 03 0 4 Li 205 Mn 176 Ni 020 O 4 90%
  • Example 2 LiMn 185 Al 0. 12 Li 0O3 O 4 without 76%
  • the present invention it is possible to provide a material for a lithium secondary battery and a lithium secondary battery which are excellent in battery characteristics at a high temperature while suppressing a decrease in performance at a high temperature (a decrease in charge / discharge cycle under a high temperature condition). it can.

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Abstract

L'invention concerne un matériau d'électrode positive destiné à un accumulateur au lithium comprenant (1) un oxyde composite au lithium-manganèse ayant une structure à spineller dans laquelle une partie des sites Mn est remplacée par un autre élément et (2) un composé ayant une structure obtenue par substitution d'un élément différent de Li à une partie des sites Mn d'un oxyde composite au lithium-manganèse à système tétragonal représenté par Li2Mn2O4 et/ou un oxyde composite au lithium-manganèse ayant une structure en couche; une électrode positive destinée à un accumulateur au lithium contenant ledit matériau d'électrode positive pour un accumulateur au lithium constituant son matériau actif; et un accumulateur au lithium doté de ladite électrode positive en temps qu'accumulateur au lithium. Le matériau de l'électrode positive destiné à un accumulateur au lithium peut être utilisé pour supprimer la diminution des capacités de rendement à haute température telle que la diminution de la capacité due au cycle répété de charge/décharge d'un accumulateur sous haute température et ainsi pour produire un accumulateur au lithium présentant d'excellentes caractéristiques dans des conditions de température élevée.
PCT/JP2000/005338 1999-08-19 2000-08-09 Materiau d'electrode positive pour accumulateur au lithium et electrode positive, et accumulateur au lithium WO2001015252A1 (fr)

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Cited By (3)

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WO2003009407A2 (fr) * 2001-07-14 2003-01-30 The University Court Of The University Of St Andrews Ameliorations concernant des cellules electrochimiques
WO2003015198A2 (fr) * 2001-08-07 2003-02-20 3M Innovative Properties Company Compositions de cathode destinees a des accumulateurs lithium ion
US8241791B2 (en) 2001-04-27 2012-08-14 3M Innovative Properties Company Cathode compositions for lithium-ion batteries

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JPH087883A (ja) * 1994-06-23 1996-01-12 Sony Corp 非水電解液二次電池
JPH09306475A (ja) * 1996-05-15 1997-11-28 Sanyo Electric Co Ltd リチウムイオン電池及びその製造方法
JPH10149828A (ja) * 1996-11-18 1998-06-02 Toshiba Battery Co Ltd リチウム二次電池
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US8241791B2 (en) 2001-04-27 2012-08-14 3M Innovative Properties Company Cathode compositions for lithium-ion batteries
WO2003009407A2 (fr) * 2001-07-14 2003-01-30 The University Court Of The University Of St Andrews Ameliorations concernant des cellules electrochimiques
WO2003009407A3 (fr) * 2001-07-14 2004-10-28 Univ St Andrews Ameliorations concernant des cellules electrochimiques
WO2003015198A2 (fr) * 2001-08-07 2003-02-20 3M Innovative Properties Company Compositions de cathode destinees a des accumulateurs lithium ion
WO2003015198A3 (fr) * 2001-08-07 2004-04-01 3M Innovative Properties Co Compositions de cathode destinees a des accumulateurs lithium ion

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