WO2001077023A1 - Oxyde a complexe de lithium/manganese, son procede de production et pile au lithium l'utilisant - Google Patents

Oxyde a complexe de lithium/manganese, son procede de production et pile au lithium l'utilisant Download PDF

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Publication number
WO2001077023A1
WO2001077023A1 PCT/JP2001/002952 JP0102952W WO0177023A1 WO 2001077023 A1 WO2001077023 A1 WO 2001077023A1 JP 0102952 W JP0102952 W JP 0102952W WO 0177023 A1 WO0177023 A1 WO 0177023A1
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Prior art keywords
lithium
composite oxide
manganese composite
coating layer
manganese
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PCT/JP2001/002952
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English (en)
Japanese (ja)
Inventor
Tokuo Suita
Hiromitu Miyazaki
Kenji Kataoka
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Ishihara Sangyo Kaisha, Ltd.
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Priority to AU46840/01A priority Critical patent/AU4684001A/en
Publication of WO2001077023A1 publication Critical patent/WO2001077023A1/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
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium-manganese composite oxide, which is a compound useful as a positive electrode material of a lithium battery, a method for producing the same, and a lithium battery using the same.
  • Lithium secondary batteries have been rapidly spreading in recent years because of their high voltage, excellent charge / discharge cycle characteristics, light weight, and small size. In particular, batteries with a high electromotive force of 4 V class are required. As such a lithium secondary battery, one using a composite oxide of cobalt or nickel ⁇ / and lithium as a positive electrode active material is known. However, cobalt and nickel are expensive, and future resources Is a problem.
  • the lithium manganate represented by the above chemical formula has a stoichiometric composition, and a 4 V class lithium battery using this as a positive electrode active material has a theoretical capacity of 148 mAhZg.
  • lithium secondary batteries using such lithium manganate do not have sufficient cycle characteristics and storage characteristics especially at high temperatures. For example, at 50 ° C or higher, the battery capacity increases when charging and discharging are repeated. Therefore, lithium manganate having excellent characteristics at high temperatures has been demanded.
  • 2000-169,152 discloses that lithium and manganese composite oxide particles and a cobalt compound are oxidized in an alkaline aqueous solution at 20 to 100 ° C.
  • a cobalt-adhered lithium-manganese composite oxide in which a cobalt oxide is epitaxially grown on a cobalt-manganese composite oxide is disclosed, but there is a problem that the charge / discharge capacity is reduced.
  • the present invention overcomes the above-described problems of the prior art, and provides a deposited lithium-manganese composite oxide having excellent high-temperature characteristics and high charge / discharge capacity suitable for a lithium battery, and an industrial and economical method for producing the same. It is intended to provide a method for producing in an advantageous manner.
  • the present inventors have applied a crystalline coating layer having the same crystal structure to the surface of the lithium-manganese composite oxide, and this coating layer has at least a specific element. It has been found that if manganese is contained, not only at room temperature but also at high temperature, the properties are excellent in storage properties and storage stability, and the charge / discharge capacity does not decrease.
  • the present invention relates to a lithium-manganese composite oxide having a coating layer on the surface, wherein the coating layer comprises at least one metal element selected from the group consisting of Co, Fe and Ni and Mn.
  • Lithium-manganese composite oxide characterized by having the same crystal structure as the crystal contained in the lithium-manganese composite acid, a method for producing the same, and a lithium-manganese composite using the same
  • the present invention relates to a lithium battery using an oxide.
  • Figure 1 is an X-ray chart of Sample B and Sample H.
  • the lithium-manganese composite oxide of the present invention has a surface on which a coating layer containing at least one metal element selected from the group consisting of Co, Fe and Ni and at least Mn is adhered.
  • This coating layer is crystalline and has the same crystal form as the lithium-manganese composite acid. It not only has excellent high temperature properties, but also has Has almost no decrease and has good battery characteristics inherent to lithium-manganese composite oxide. The reason for this is not always clear, but generally the cycle and storage characteristics are degraded because manganese ions elute from the contact interface between the lithium-manganese composite oxide and the electrolyte. It is said that this phenomenon becomes significant especially at high temperatures.
  • the present invention there is almost no difference in the lattice constant between the coating layer and the lithium-manganese composite oxide, and since these are crystals having a continuous structure, the adhesion is excellent, and the surface of the lithium-manganese composite oxide is excellent. It is considered well protected. On the other hand, even if the surface is covered by the coating layer, the inclusion and desorption of lithium ions is hardly inhibited by the inclusion of the metal element and Mn in the coating layer, and the charge / discharge capacity is not reduced. It is guessed.
  • the composition of the coating layer does not need to be uniform.
  • Mn in the coating layer may have a concentration gradient or Mn may exist randomly.
  • the metal element may be contained in the coating layer as a compound such as an oxide, and Mn may be contained as a single compound such as an oxide or a compound compound such as a composite oxide with the metal element. Is good and there is no particular limitation.
  • the crystal form of the coating layer is not particularly limited as long as it is the same form as the lithium-manganese composite oxide, but as described later, the lithium-manganese composite oxide is preferably a spinel type, and thus has the same spinel type. Is preferred.
  • a portion having a different amorphous or crystalline form may be contained as a production impurity in a small amount, preferably 5% or less.
  • the Chakuryou metal element contained in the coating layer is a 0.05 to 20 atomic 0/0 relative to the total amount of the M n of the lithium-manganese composite oxide ⁇ Pi coating layer, the deposition amount of 0.05 atoms 0 / lower the desired effect can not be obtained from 0, more preferably in the range of 0.1 to 10 atomic% Deari, more preferably from 1 to 5 atomic% 0.1.
  • the amount of Mn contained in the coating layer is a C o, F e, 0.
  • Co 1 ⁇ 50 atomic with respect to the total amount of the N i 0/0.
  • at least one of Co, Fe, and Ni may be used, and two or three of them may be used in combination. Among them, Co is particularly effective.
  • Elements other than Co, Fe, Ni, and Mn can be appropriately included in the coating layer for various purposes. Examples of such elements include Mg, Ca, V, Cu, Zn, and Li. The amount of these elements contained in the coating layer is, for example, based on the total amount of Co, Fe, and Ni. 0. 0 to 50 atoms 0 / o.
  • Such a coating layer may be applied to the lithium-manganese composite oxide by reacting the compound containing the metal element and the compound containing Mn with a basic compound.
  • the coating layer is applied under a strong alkaline condition in which free monohydric ion is 0.001 mol Z liter or more.
  • the compound containing at least one metal element selected from the group consisting of Co, Fe and Ni in the slurry containing the lithium-manganese composite oxide, and a basic compound Is added so that the concentration of free monohydric acid becomes 0.001 mol Z liter or more, and contains at least one kind of the metal element, and preferably contains at least one kind of the metal element.
  • a coating layer containing Mn is applied.
  • the lithium-manganese composite oxide is uniformly dispersed in a medium such as an organic solvent, preferably in water, to prepare a slurry containing the same.
  • a medium such as an organic solvent, preferably in water
  • wet pulverization or sizing may be appropriately performed by a known method using a disperser such as a line mill, a sand mill, or a pole mill.
  • a solution of a compound containing one kind of metal element selected from the group consisting of Co, Fe and Ni and a basic compound are added to the slurry to form a mixture of free hydroxide in the slurry.
  • the metal element compound to be added include salts such as chlorides, sulfates, nitrates, acetates, and carbonates, and hydroxides, oxyhydroxides, and oxides. Oxides and carbonates can be used.
  • a method of adding these compounds a method of adding a basic compound first and then simultaneously adding a solution of a metal compound is preferable because both are uniformly coated.
  • the salt of Co, Fe, and Ni reacts with the basic compound to precipitate as a hydroxide, an oxyhydroxide or an oxide, and has a free hydroxyl ion concentration of 0.000. When it exceeds 0 mol / liter, complexation of these compounds proceeds.
  • a hydroxide, an oxyhydroxide, or an oxide of the metal element is added to the slurry, a complex is formed in the presence of 0.0001 mol / liter or more of free hydroxyl ions. .
  • this method (1) forming a crystalline coating layer on the surface while the complex reacts with a part of manganese in the lithium-manganese composite oxide; (2) After the complex forms a crystalline coating layer, part of the manganese in the lithium-manganese composite oxide diffuses into the coating layer. (3) Part of manganese from the lithium-manganese composite oxide under strong alkalinity Is eluted, and manganese and the complex react to form a further complex to form a crystalline coating layer. Therefore, a complexing agent such as ammonia or EDTA may be added during the deposition process.
  • the deposition treatment can be usually performed at a temperature of 25 to 200 ° C.
  • the atmosphere for the deposition treatment is not particularly limited. However, when the deposition is performed in a non-oxidizing atmosphere by blowing an inert gas such as nitrogen into the slurry, the compound of the added metal element reacts. This is preferable because the reaction is not easily performed before the reaction and the reaction easily proceeds.
  • the free hydroxyl ion referred to in the present invention refers to a hydroxyl ion present in a slurry after a predetermined amount of a metal compound and a basic compound have been added. If the free hydroxyl ion concentration is lower than 0.001 mol Z liter, the formation of a coating layer of a metal compound is not sufficient, and good high-temperature characteristics cannot be obtained. When the concentration of free hydroxyl ions is increased, the coating layer aimed at by the present invention can be formed in a short time, but the effect is saturated when the concentration is 5 mol Z liter or more, which is not industrially advantageous.
  • the range of the free hydroxyl ion concentration is 0.001 to 5 mol / L, preferably 0.001 to 3 mol / L, and more preferably 0.01 to 2 mol / L.
  • the deposition treatment is performed by this method, the lithium manganese composite acid may be partially reduced, which is not preferable in terms of battery characteristics. Therefore, after the deposition, the deposition is performed in a slurry or in the air. It is preferable to oxidize. Thereafter, filtration and washing are appropriately performed, and drying is performed at 50 to 200 ° C, preferably 90 to 150 ° C. Drying may be performed in an oxidizing atmosphere such as the air or a non-oxidizing atmosphere such as nitrogen.
  • the dried lithium manganese composite oxide that has been subjected to the deposition treatment after drying may be subjected to a powder frame depending on its aggregation state.
  • Lithium 'manganese Sani ⁇ used in the present invention has the general formula L i x M n y 0 4 or Chopsticks i 1 + x M y Mn 2 -x-y0 4 was (M is F e, C r, Co, Ni, A 1, Mg, Ca, B, Zn, V, Nb, Mo, T i, Z r, at least one metal element selected from the group consisting of Ga and In) wherein X and Y in the formula are (1 + X) / (2-XY) Expressed in the range of 0.3 to 1.5 is a preferred composition.
  • L iMn 2 0 4 preferably has a L i 4/3 Mn 5/3 0 4 spinel crystal structure which is Ru represented by like, a single phase of the lithium-manganese composite oxide Alternatively, a mixture of a lithium * manganese composite oxide and a manganese oxide may be used.
  • the method for producing such a lithium-manganese composite oxide there is no particular limitation on the method for producing such a lithium-manganese composite oxide, and even if manganese oxide and a lithium compound are mixed and then heated and baked, the manganese oxide reacted with a manganese oxide or acid can be used.
  • One of arsenic or manganic acid and a lithium compound may be reacted in a medium such as water, and the resulting precursor of the lithium-manganese composite oxide may be heated and fired.
  • the latter method is preferable because a lithium-manganese composite oxide having excellent crystallinity can be obtained.
  • Manganese oxide or manganic acid which has been previously reacted with an acid has good reactivity with a lithium compound. It is more preferable to use this.
  • lithium-manganese composite oxide that has been subjected to the deposition treatment has excellent filling properties as a positive electrode active material.
  • lithium-manganese composite acid may be sintered to grow the particles, but manganese oxide is used as a seed (a nucleus or a seed crystal is hereinafter referred to as a seed). It is preferred that the particles be grown in a medium and then reacted with a lithium compound, since a crystal having good crystallinity and a uniform particle size / size distribution can be obtained.
  • the present invention is a lithium battery using the above-described lithium-manganese composite oxide as a positive electrode active material.
  • a lithium battery as referred to in the present invention is a primary battery using lithium metal for the negative electrode, a rechargeable battery using lithium metal for the negative electrode, a charging using a carbon material, a tin compound, lithium titanate, or the like for the negative electrode.
  • the lithium-manganese composite acid powder of the present invention may be added to a carbon-based conductive agent such as acetylene black, carbon, or graphite powder, or a polycondensate. It can be obtained by adding, kneading, and molding a binder such as tetrafluoroethylene resin or polyvinylidene fluoride resin.
  • a binder such as tetrafluoroethylene resin or polyvinylidene fluoride resin.
  • an organic solvent such as N-methylpyrrolidone is added to the lithium and manganese composite oxide powder of the present invention in addition to these additives, and the mixture is kneaded. Into a paste, applied to a metal current collector such as an aluminum foil, and dried.
  • Lithium ion is dissolved in the electrolyte of a lithium battery in a polar organic solvent that is electrochemically stable, that is, is not oxidized or reduced in a wider range than the potential range that operates as a lithium ion battery. Things can be used.
  • a polar organic solvent propylene carbonate, ethylene carbonate, getylcaponate, dimethoxetane, tetrahydrofuran, ⁇ -butyltyl lactone, or a mixture thereof can be used.
  • As a solute serving as a lithium ion source lithium perchlorate / lithium hexafluorophosphate, lithium tetrafluoroborate, or the like can be used.
  • a porous polypropylene film / polyethylene film is disposed as a separator between the electrodes.
  • Battery types include a separator between the positive and negative electrodes in the form of pellets, pressure bonding to a sealed can with a polypropylene gasket, injection of electrolyte, and a sealed coin-type battery.
  • the negative electrode material is coated on a metal current collector, the separator is sandwiched and wound, inserted into a battery can with a gasket, injected with an electrolyte, and sealed.
  • a secondary battery is constructed using metal lithium or the like as the negative electrode, and charged and discharged at an appropriate voltage range with constant current.
  • the capacity can be measured. Further, by repeating charge and discharge, it is possible to judge the quality of the cycle characteristics from the change in the capacity.
  • the precursor of the lithium-manganese composite oxide was dried at 110 ° C for 12 hours, and then calcined in air at 750 for 3 hours to obtain a lithium-manganese composite oxide.
  • the specific surface area of the lithium-manganese composite acid was 0.94 m 2 / g.
  • Lithium-manganese composite acid (200 g in terms of Mn) was dispersed in water with a mixer to form a slurry, and then charged into a reaction vessel. Next, 95.2 milliliters of a 4.5 molar Z liter aqueous lithium hydroxide solution was added to adjust the liquid volume to 1.00 liter. After nitrogen gas was blown into the slurry and the temperature was raised to 60 ° C., 128.5 milliliters of a 50 g / litre aqueous solution of sodium salt as a copart was added over 1 hour, reacted for 5 hours, and cooled.
  • lithium-manganese composite oxide precursor was heated and calcined in the same manner as in the sixth step of Example 1 to obtain a lithium-manganese composite oxide.
  • the specific surface area of this lithium-manganese composite oxide was 1.01 m 2 Zg.
  • Lithium manganese composite oxide obtained in the second step of Example 2 (converted to Mn)
  • Co and Co were prepared in the same manner as in the third step of Example 2 except that the lithium manganese composite oxide obtained in the second step of Example 2 was used, and the addition amount of the lithium hydroxide aqueous solution was 233.8 milliliters. A lithium manganese composite oxide treated with a coating layer compound containing Mn was obtained. (Trial D) The addition amount of lithium hydroxide was set so that the concentration of free monohydric ion after reaction with cobalt salt was 0.80 mol.
  • lithium 'manganese composite oxide obtained in the second step of Example 2 after reacting salt sodium hydroxide and lithium hydroxide, air was passed through the slurry at 1 liter / min for 3 hours.
  • a lithium-manganese composite oxide treated with a coating layer compound containing Co and Mn was obtained in the same manner as in the third step of Example 2 except that the oxidation was performed.
  • Example G Comparative Example 2
  • a lithium-manganese composite oxide was obtained in the same manner as in Example 2, except that the coating treatment including the Co and Mn in the third step was not performed. (Sample H) Comparative Example 3
  • the lithium-manganese composite oxide (200 g in terms of Mn) obtained in the second step of Example 2 was dispersed in water with a mixer to form a slurry, and then charged into a reaction vessel. Next, 4.51 milliliters of an aqueous lithium hydroxide solution (26.1 milliliters) was added to adjust the liquid volume to 1.0 liters. While blowing nitrogen gas into this slurry, 50 g Z liters of a salt solution of 93.3 milliliters of an aqueous solution of cobalt were added as a co-part, and then 90. The temperature was raised to C, and the nitrogen gas was stopped after the temperature was raised.
  • Figure 1 shows the powder X-ray diffraction patterns of Samples B and H, and Table 1 shows the results. None of the samples showed a diffraction peak of spinel alone and no power was recognized.
  • the coating layer of the present invention By applying the coating layer of the present invention to the surface, the diffraction angle shifts to the lower angle side, and the half width tends to increase.
  • the peak area some peaks, such as the main peak, show a decreasing trend, while others show an increasing trend.
  • the diffraction peak of the plane index (220) showed the largest increasing tendency.
  • the actual composition of the coating layer is not always a stoichiometric composition as in the above formula, and a spinelidized product having a wider composition containing manganese and cobalt / reto, and in some cases containing lithium may be formed. It is thought that it is.
  • EDX analysis was performed on Sample B inside a few nm from the outermost surface of the particles, that is, a portion corresponding to the coating layer. Table 2 shows the results. EDX analysis also shows that Co and Mn exist in the coating layer.
  • the positive electrode was vacuum-dried at 120 ° C for 4 hours, and then incorporated into a sealable coin-type evaluation cell in a glove box with a dew point of 70 ° C or less.
  • the evaluation cell used was made of stainless steel (SUS 316) and had an outer diameter of 20 mm and a height of 1.6 mm.
  • the negative electrode used was 0.5 mm thick metallic lithium molded into a 14 mm diameter circle.
  • the positive electrode was placed in the lower can of the evaluation cell, a porous propylene film was placed thereon as a separator, and seven drops of a non-aqueous electrolyte were dropped from above with a dropper.
  • the negative electrode was placed on top of it, and an upper can with a gasket made of polypropylene was covered, and the outer peripheral edge was crimped and sealed.
  • a hydrophilic non-woven polypropylene nonwoven fabric was placed above and below the separator as necessary.
  • the coin-type evaluation cell thus fabricated was set in a special battery holder, and the battery characteristics were measured with a load of 5 kg applied.
  • the charge / discharge capacity was measured at a constant current with the voltage range set from 4.3 V to 3.5 V and the charge / discharge current set at 0.84 mA (about 3 cycles / day).
  • the values measured in the second cycle at 25 ° C are used as initial charge / discharge characteristics. did.
  • the cycle characteristics were measured at 25 ° C. and 50 ° C., and represented by the respective capacity retention rates% ⁇ (30th discharge capacity Z 5th discharge capacity) ⁇ 100 ⁇ .
  • Table 3 shows the initial charge / discharge characteristics, cycle characteristics, and manganese elution amount of Samples A to I.
  • the lithium-manganese composite oxide having a coating layer containing Co or Fe and Mn obtained on the surface thereof obtained by the present invention is subjected to a deposition treatment especially at a high temperature cycle 4. It is superior to non-lithium-manganese composite oxide and has the same initial charge / discharge characteristics. In addition, both the cycle characteristics and the initial charge / discharge characteristics are better than those with the conventional Co coating applied to the surface. Furthermore, from any of the comparative examples
  • the present invention relates to a lithium-manganese composite oxide having a coating layer on its surface
  • the coating layer contains at least one metal element selected from the group consisting of Co, Fe, and Ni and Mn, and has a crystal structure identical to the crystal contained in the lithium-manganese composite oxide. Is a lithium-manganese composite oxide.
  • the lithium-manganese composite oxidized product of the present invention has high adhesion of the treated coating layer, excellent protection of the particle surface, and is difficult to dissolve manganese ions even when contacted with an electrolytic solution. .
  • the deterioration of the lithium 10 manganese manganese compound becomes difficult to progress, and the lithium battery using this as a positive electrode active material has a cycle characteristic and a storage characteristic, especially at 50 ° C. Good at high temperatures.
  • this coating layer does not easily inhibit the introduction and desorption of lithium ions contained in the lithium-manganese composite oxide, the charge / discharge capacity does not decrease.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un oxyde à complexe de lithium/manganèse comprenant une couche de revêtement sur sa surface, caractérisé en ce que la couche de revêtement contient du Mn ainsi qu'au moins un élément métallique choisi dans le groupe contenant Co, Fe et Ni, et présente une structure de cristal de la même forme de cristal que celle du cristal contenu dans l'oxyde à complexe de lithium/manganèse.
PCT/JP2001/002952 2000-04-07 2001-04-05 Oxyde a complexe de lithium/manganese, son procede de production et pile au lithium l'utilisant WO2001077023A1 (fr)

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AU46840/01A AU4684001A (en) 2000-04-07 2001-04-05 Lithium/manganese complex oxide and method for producing the same, and lithium cell using the same

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JP2000-105795 2000-04-07
JP2000105795 2000-04-07

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10236826A (ja) * 1997-02-25 1998-09-08 Sakai Chem Ind Co Ltd ２層構造粒子状組成物及びリチウムイオン二次電池
JP2000100433A (ja) * 1998-09-25 2000-04-07 Toyota Central Res & Dev Lab Inc 酸化ニッケル被覆リチウムマンガン複合酸化物粉末とその製造方法
JP2000340226A (ja) * 1999-05-26 2000-12-08 Kawasaki Steel Corp リチウムマンガン複合酸化物粒子およびその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10236826A (ja) * 1997-02-25 1998-09-08 Sakai Chem Ind Co Ltd ２層構造粒子状組成物及びリチウムイオン二次電池
JP2000100433A (ja) * 1998-09-25 2000-04-07 Toyota Central Res & Dev Lab Inc 酸化ニッケル被覆リチウムマンガン複合酸化物粉末とその製造方法
JP2000340226A (ja) * 1999-05-26 2000-12-08 Kawasaki Steel Corp リチウムマンガン複合酸化物粒子およびその製造方法

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