WO2000058221A1 - Compose de manganese particulaire et son procede de preparation, et cellule secondaire utilisant ce compose - Google Patents

Compose de manganese particulaire et son procede de preparation, et cellule secondaire utilisant ce compose Download PDF

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Publication number
WO2000058221A1
WO2000058221A1 PCT/JP2000/001856 JP0001856W WO0058221A1 WO 2000058221 A1 WO2000058221 A1 WO 2000058221A1 JP 0001856 W JP0001856 W JP 0001856W WO 0058221 A1 WO0058221 A1 WO 0058221A1
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Prior art keywords
manganese
lithium
less
oxide
density
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PCT/JP2000/001856
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English (en)
Japanese (ja)
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Yoshio Kajiya
Hiroshi Tasaki
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Japan Energy Corporation
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Priority claimed from JP08511499A external-priority patent/JP3495639B2/ja
Priority claimed from JP11085093A external-priority patent/JP2000281347A/ja
Priority claimed from JP08510699A external-priority patent/JP3495638B2/ja
Priority claimed from JP2000043588A external-priority patent/JP3495676B2/ja
Application filed by Japan Energy Corporation filed Critical Japan Energy Corporation
Publication of WO2000058221A1 publication Critical patent/WO2000058221A1/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
    • H01M4/36—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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • 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, for example, manganese dioxide (MnO 2) used as a positive electrode of a manganese primary battery and a lithium-manganese composite oxide (Li xMn! O 4 ) used as a positive electrode of a lithium secondary battery.
  • MnO 2 manganese dioxide
  • Li xMn! O 4 lithium-manganese composite oxide
  • Spherical, high-density fine manganese carboxylate suitable as a raw material for producing LiMnO, LiMn! OJ, etc.
  • the present invention relates to a lithium secondary battery using a lithium-manganese composite oxide as a positive electrode active material and having excellent cycle characteristics at high temperatures.
  • CMD Chemical manganese dioxide
  • Electrolytic manganese dioxide obtained by electrolytically treating a soluble manganese salt solution.
  • manganese dioxide for batteries is mainly used as the positive electrode of primary batteries, the good fluidity required to fill the mold for forming the positive electrode with high density and the high fluidity required Packing density is required.
  • electrolytic manganese dioxide although the apparent density is as high as 2.5 g / cm s due to the characteristics of the manufacturing method, the shape becomes irregular when crushed to a predetermined particle size, Therefore, it was inferior in fluidity and it was difficult to achieve a sufficiently high packing density.
  • CMD chemical manganese dioxide
  • the manganese dioxide obtained in this way has a spherical It has good properties and is therefore rich.
  • the conventional chemical manganese dioxide has a relatively large particle size and, therefore, a low apparent density.Therefore, when used as a battery cathode, there is a problem in that the apparent density must be increased by performing heavy treatment. Was.
  • Li lithium secondary battery has emerged as a solution that can solve the problem pointed out in the conventional secondary battery that "the discharge voltage is low and the weight reduction is difficult”.
  • This "lithium rechargeable battery” has a higher energy density than nickel-powered dommium batteries and nickel-hydrogen batteries, etc., and can further reduce the weight and life of the equipment.
  • this lithium secondary battery has three basic components: the “positive electrode”, the “negative electrode”, and the “separate holding electrolyte” interposed between the two electrodes. It is composed of elements.
  • the positive electrode and the negative electrode are made of a metal foil, metal mesh, etc., made of a slurry made by mixing and dispersing an active material, a conductive material, a binder and, if necessary, a plasticizer in a dispersion medium.
  • the one coated on the current collector is used.
  • lithium-cobalt composite oxide (LiCoO,) has been mainly used as the positive electrode active material.
  • the negative electrode active material a material capable of inserting and extracting lithium ions (for example, a carbon material such as coke-based carbon and graphite-based carbon) is used.
  • a carbon material such as coke-based carbon and graphite-based carbon
  • the conductive material a substance having electronic conductivity (for example, natural graphite, carbon black, acetylene black, etc.) is used, and as the binder, polytetrafluoroethylene (PTFE), polyfluorinated polyethylene is used.
  • PTFE polytetrafluoroethylene
  • Fluorinated resins such as vinylidene (PVDF) and hexafluoropropylene (HFP) and copolymers of these resins are used.
  • an organic solvent capable of dissolving the binder for example, acetone, methylethylketone (MEK), tetrahydrofuran (THF), dimethylformamide, dimethylacetamide, tetramethyl Lamethylurea, trimethyl phosphate, N-methylpyrrolizone (NMP) and the like are used.
  • an “organic solvent” that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film is appropriate.
  • an “organic solvent” that can be replaced with an electrolyte after the slurry is applied to the current collector and formed into a film.
  • the current collector to which the slurry is applied stainless steel, nickel, aluminum, titanium, copper punched metal and expanded metal are preferable, and a material obtained by applying a surface treatment to these materials is preferable. Can also be used.
  • the slurry required for coating is adjusted by kneading the active material, conductive material, binder, dispersion medium and plasticizer at a predetermined ratio.
  • Various coating methods such as gravure coating, blade coating, comma coating, and dip coating can be applied to the coating on the current collector.
  • liquid, polymer or solid electrolytes are known as the electrolyte to be retained in the separator, but a liquid composed of a solvent and a lithium salt dissolved in the solvent is known.
  • the solvent may be polyethylene carbonate, ethylene carbonate, dimethyl sulfoxide, butyl lactone, sulfolane, 1,2-dimethyl methoxyethane, tetrahydrofuran, Jechiruka one Bone DOO, main Chiruechiruka one Bonnet one Bok, an organic solvent of dimethyl carbonate Natick Bok etc. suitable, in the Matari lithium salt Li CF S S 0 ,, LiAsF LiCI O ,, Li ⁇ F ,, Li PF 4 and the like are preferred.
  • Lithium-manganese composite oxides (LixMn! O,) and lithium'nickel composite oxides (LiNi0) have been studied as substances.
  • LiMnO Lithium-manganese composite oxides
  • LiMn z Li Chiu ⁇ manganese composite oxide such as 0 (Li xMn! O,) is not only advantageous in abundance Ya cost Bok of view of resources, discharge voltage It has received much attention due to its high cost and relatively high thermal stability of the state of charge.
  • lithium manganese composite oxide (LixMn! O j Reaction of the above-mentioned electrolytic manganese dioxide (EMD) or chemical manganese dioxide (CMD) or "manganese oxide” such as ⁇ , ⁇ , ⁇ , etc. obtained by heat treatment with “lithium compound” such as lithium carbonate. It is known that it can be easily manufactured by performing the above.
  • Various manganese dioxides ⁇ ⁇ ⁇ ⁇ !), Such as synthetic manganese dioxide, and dimanganese trioxide (, ⁇ , ,,) obtained by heat treatment of these manganese dioxides are mainly used.
  • These manganese oxide materials were said to exhibit good fluidity and high packing density required for a raw material for producing lithium ⁇ manganese composite oxide for lithium secondary batteries.
  • the manganese oxide which is considered to have good fluidity and high packing density, has a relatively large particle size (maximum particle size 100 m or more, average particle size 25 um or more).
  • maximum particle size 100 m or more, average particle size 25 um or more When an electrode for a lithium secondary battery is manufactured using a material having such a large particle size as a raw material, there is a problem that it is difficult to obtain a practically smooth electrode.
  • a solution containing a manganese salt is infiltrated into the vacancies of manganese oxide, and then the solvent is evaporated, and then the manganese salt remaining in the vacancies using chlorine gas or the like. Oxidation method is used ing.
  • lithium composite oxide (L i x MO,: M is a transition metal, and the average particle size of 0.05 ⁇ X ⁇ 1.10) is restricted to 10 to 150 m, and particles less than 5 m are suppressed to less than 30% by volume. It has been proposed.
  • lithium-manganese composite oxide as fine as possible in lithium secondary batteries that use lithium-manganese composite oxide as the positive electrode from the viewpoint of battery characteristics.
  • lithium and manganese composite oxides having a maximum particle size of 30 m or less or 20 m or less and a median diameter of 10 m or less have been desired from the viewpoint of battery characteristics.
  • Such lithium ⁇ manganese compound As a raw material for producing a composite oxide, "fine manganese carbonate with a spherical shape with excellent fluidity and a maximum particle size of 30 m or less or 10 nm or less and a median diameter of 10 m or less" is desired. It has come to be.
  • the shape and particle size of the “lithium-manganese composite oxide” that can be easily produced by reacting manganese dioxide with lithium carbonate are based on the raw material manganese dioxide and manganese dioxide.
  • the use of “fine manganese carbonate particles consisting of a single spherical particle” as the raw material for production makes it possible to obtain lithium secondary batteries with satisfactory battery characteristics, since they are almost inferior to the manganese carbonate that is the raw material for production. This is because batteries can be obtained.
  • Stable and fine-grained manganese carbonate suitable for the production of, for example, “manganese dioxide for batteries” and “lithium-manganese composite oxide used as the positive electrode of lithium secondary batteries” Establish means that can be realized.
  • a high-density fine-grained manganese oxide suitable for the production of lithium manganate which has the “fine” and “high tap density” required for the cathode material of lithium secondary batteries, is stable and low-cost.
  • Lithium exhibiting satisfactory battery characteristics (various battery characteristics including high-temperature cycle characteristics) when applied to, for example, a positive electrode active material for lithium secondary batteries.
  • Lithium manganese composite oxide (LixMn) , 0 4 ) Lithium manganese composite oxide (LixMn) , 0 4 ), and a lithium secondary battery with excellent battery characteristics is provided by using this. Disclosure of the invention The present inventors have increasingly found that “spheroidal and fine-grained carbon dioxide suitable for producing“ manganese dioxide for batteries ”and“ lithium-manganese composite oxide used as a positive electrode of lithium secondary batteries ”and the like. As a result of diligent research in search of a means for stably realizing manganese '', the following series of items (a) to (d) were found.
  • the aqueous solution of ammonium salt dissolves metal manganese.
  • metal manganese For example,
  • the reaction produces manganese carbonate.
  • the manganese carbonate thus produced has a spherical particle shape, a maximum particle size of 30 3m or less or 20 ⁇ m or less, and a median diameter of
  • the tap density is high enough to satisfy 10 m or less. It is possible to obtain a manganese oxide having good fluidity and a high apparent density by calcining the manganese oxide, and heat-treating this manganese oxide together with a lithium salt to cause a reaction. ⁇ Manganese composite oxide can be produced.
  • Fine grains are formed.
  • the tap density of the obtained manganese oxide ( ⁇ , ⁇ ,) shows a remarkable tendency to increase compared to the conventional manganese oxide. Absent.
  • Manganese carbonate (MnC 0) was used as a starting material, which was first heat-treated in a low oxidizing atmosphere (oxygen concentration less than 15%).
  • the tap density is a very high value 1.2 g / cm s or more, and even 1.8 g / cm 'or more, it is possible to obtain fine-grained high-density manganese oxide ( ⁇ , ,,), which is used as a raw material for producing lithium manganate for lithium secondary batteries. In such a case, the performance of the obtained product is greatly improved.
  • the production method of fine-grain manganese carbonate proposed as 1 0 — 3700 0 20 is based on the reaction of “manganese carbonate by reacting divalent manganese ion with carbonic acid or hydrogen carbonate ion.
  • the reaction is carried out in the presence of ammonia water ".
  • ammonia (100% NH, converted) in the coexisting ammonia water and divalent manganese ion are used. It is advisable to adjust the molar ratio (N ⁇ , / ⁇ 2.5 + ) to 2.5 or more.
  • the tap density is high (a tap density of 1.8 g / cm s or more can be achieved sufficiently). It is possible to obtain high-density manganese oxide particles ( ⁇ , ⁇ ,), and more preferably, it is easy to obtain high-density manganese oxide particles ( ⁇ , 0) having a spherical particle shape.
  • spherical lithium having a median diameter of 10 m or less can be manufactured stably. By doing so, a lithium secondary battery with excellent battery characteristics including cycle characteristics at high temperatures is realized.
  • the present invention has been completed on the basis of the above findings and the like, and includes the following fine-grained manganese carbonate (MnC 0 s), its production method, and fine-grained high-density manganese oxide (Mn, 0 s ). and a manufacturing method thereof, there is provided a lithium secondary battery using the fine particle lithium ⁇ manganese composite oxide (Li x Mn, 0 4) and a method for manufacturing the same, and the fine granules lithium. manganese composite oxide.
  • Fine-grained manganese carbonate having a spherical particle shape, a median diameter of 1 O ⁇ m or less, and a tap density of 1.2 g / cm s or more.
  • the solution is characterized by blowing C 0 gas into the solution in the pH range of 8.5 or more.
  • the particle shape is spherical, the median diameter is 10 m or less, and the evening density is 1.2 g. / cm: A method for producing fine-grained manganese carbonate showing the above.
  • Fine-grain, high-density manganese oxide having a median diameter of 10 m or less and a tap density of 1.8 g / cm 'or more.
  • particle shape is spherical, the 5) fine grain high-density oxide manganese according to claim 0
  • Lithium-Manganese composite oxide characterized by a chemical composition of Li x Mn, 0, (1.0 ⁇ x ⁇ 1.2) and a spherical shape with a median diameter of 10 m or less .
  • LiJn! O (1.0 ⁇ x ⁇ ), characterized by mixing and firing manganese oxide with a median diameter of 10 ⁇ m or less and a lithium compound.
  • the manganese oxide as a firing raw material has a spherical particle shape, 17). 3. The method for producing a lithium'manganese composite oxide according to claim 1.
  • Manganese oxide the raw material for calcination, is obtained by heat-treating manganese carbonate with a spherical shape at a temperature of 400 to 800 ° C in an atmosphere with an oxygen concentration of less than 15%, and then further increasing the oxygen concentration to 15%. %)
  • a lithium manganese composite oxide with a chemical composition of Li Jn! O, (1.0 ⁇ x ⁇ 1.2) and a spherical shape with a median diameter of 10 m or less is applied.
  • FIG. 1 shows the ammonia fraction UN H s ] in the solution ([NH S ] + [NH :!)] and the carbonate ion fraction ⁇ [C 0 —] no ([C 0] + [HC 0 , —]) ⁇ And the relationship between pH and pH.
  • FIG. 2 is a SEM photograph of the fine-grained manganese carbonate obtained in “Example 1” described later.
  • FIG. 3 is a SEM photograph of the fine manganese carbonate obtained in “Example 4” described later.
  • FIG. 4 is a SEM photograph of the fine-grained manganese oxide obtained in “Example 7” described later.
  • FIG. 5 is an SEM photograph of the fine-grained lithium ⁇ mangan composite oxide (LiJn! O 4 ) obtained in “Example 9” described later.
  • Fig. 6 is a graph comparing the cycle test results of the lithium batteries prepared in “Example 9", “Example 10", and “Comparative Example 4" described below.
  • the median diameter was limited to 10 m or less and the tap density was limited to 1.2 g / cm 'or more.
  • the diane diameter is 10 ⁇ m or less (preferably 8 ⁇ m or less, more preferably 6 m or less) and the tap density becomes 1.2 g / cm 3 or more, this is reduced to manganese dioxide for manganese primary batteries, for example.
  • LiMnO for lithium secondary batteries This is because when used as a raw material for producing a lithium-manganese composite oxide such as LiMn: 0, etc., the battery characteristics (current load characteristics, cycle characteristics, etc.) are significantly improved.
  • Spherical fine-grained manganese carbonate as described above can be produced by dissolving metallic manganese in an ammonia-containing solution and then blowing CO and gas into this solution.
  • the form is not particularly limited, and may be any form such as "flaky", “powder”, or "dust".
  • ammonium ion (NH, +)-containing solution used for dissolving metallic manganese an aqueous solution of ammonium salt can be mentioned, but there is no particular limitation on the ammonium salt used. It may be any of NHSO, NHCI, ⁇ , ⁇ , NHCH, CO, and the like.
  • the dissolved manganese ion is stabilized by forming a complex with the produced ammonia (NH 2) in the ammonia-containing solution. That is, in the case of a solution of manganese containing no Anmoniu ⁇ ions, even manganese concentration 1 0 _ 2 mo I / degree, when the p H of about 5 8. Water manganese oxide thus precipitated promptly
  • manganese ion may form a complex with the produced ammonia alone, or manganese ion, ammonia and other ion species may form a complex.
  • manganese hydroxide does not precipitate even if the manganese concentration is as high as 1 mol / ⁇ and ⁇ ⁇ is adjusted to 8.5 or more.
  • the stabilization of manganese ions when metal manganese is dissolved depends on the concentration of ammonium ions in the solution used. That is, as the concentration of ammonia is higher, the production of manganese hydroxide is suppressed, and the manganese ion concentration region in which the manganese remains stable is increased. From such a viewpoint, the preferred ammonium ion concentration of the solution is 0.5 mol / i or more.
  • the manganese ion concentration generated by the double salt depends on the ammonium concentration, but as a result of examination, it was found that the manganese ion concentration in the above-mentioned region (the region where the ammonium ion concentration is about 0.5 mol or more) was obtained. Was found to exceed 1.5 mol / £, the formation of double salts started.
  • C 0, ⁇ ⁇ decreases with the progress of neutralization of ammonia during aeration, but as shown in Fig. 1, when pH is less than 8.5, carbonate ion becomes CO, ' — Almost nonexistent in the form of As a result, the generation rate of manganese carbonate is remarkably reduced, and the generated particles are aggregated, so that the obtained manganese carbonate has a large particle diameter and a median diameter of 10 m or less can be achieved. As a result, a tap density of 1.2 g / cm 'or more cannot be secured.
  • the initial p H of manganese carbonate production reaction should be 8.5 or higher
  • the initial p manganese carbonate formation reaction by lump can C 0 2 gas blown in order to produce a more uniform particle by increasing the reaction rate It is desirable that H be 9 or more.
  • the pH was measured at 25 ° C.
  • the manganese carbonate obtained by the above treatment is a small spherical particle having a maximum particle size of 30 ⁇ m or less, and even a small particle size of 20 ⁇ m or less, and a median diameter of 10 ⁇ m or less. Indicates 1.2 g / cm s or more. By calcining this, a manganese oxide with good fluidity and high apparent density can be obtained, and this manganese oxide is reacted with a lithium salt by heat treatment to form a lithium secondary battery. Characteristics (current load characteristics, size Lithium manganate with excellent characteristics (e.g.,
  • the fine carbonate manganese dissolution solution manganese for example, the following "C 0, gas multistage blowing method” or “solution split CO, gas multistage blowing method” the Then, the maximum particle size, median diameter, tap density, etc. of the generated fine carbonic acid manga can be controlled more finely.
  • the number of particles of manganese carbonate generated by injecting a single gas of C 0 and gas less than the equivalent of manganese is limited, and then the solution is allowed to stand for a predetermined time if necessary, and then the second time
  • CO: gas is blown
  • manganese carbonate is generated mainly using the manganese carbonate generated in the first cycle as a nucleus.
  • manganese carbonate having a somewhat increased median diameter and the like within the regulation range of the present invention is produced. Obtainable.
  • the number of times of blowing CO and gas may be appropriately determined depending on a target median diameter and the like.
  • the initial manganese dissolving solution (the manganese dissolving solution before injecting the co 2 gas) is divided into a plurality (for example, 2 to 3). divided advance, first the to produce a single manganese carbonate crowded blown C 0 2 gas into the manganese dissolution solution of a predetermined the solution then optionally After standing for a while, add another manganese dissolving solution that has been divided and separated into this manganese carbonate-containing solution, and then blow in CO and gas again.
  • the number of divisions of the manganese dissolving solution may be appropriately determined depending on the intended median diameter and the like.
  • the present invention provides a method of producing fine manganese oxide (Mn! O 5 ) having a high nip density which is unprecedented by a simple method using only manganese carbonate and a dry heat treatment. The point that it can be realized is also a big feature.
  • the dian diameter was 10 ⁇ m or less and the tap density became 1.8 g / cm 'or more, this was used as a raw material for producing lithium manganate (LiMnO 2 , LiMn.O *) for lithium secondary batteries, for example.
  • the battery characteristics current load characteristics, cycle characteristics, etc.
  • the more the shape of the manganese oxide particles is spherical the more advantageous it is to obtain these properties.
  • the manganese carbonate (MnC O,) It is necessary to select a sphere that is as uniform as possible, and take care that the heat treatment temperature when heat-treating this to obtain manganese oxide does not become excessively high.
  • Such fine-grained high-density manganese oxide is obtained by heat-treating manganese carbonate as a starting material in a low-oxidizing atmosphere, and then heat-treating it at about 530 ° C or more in an oxidizing atmosphere.
  • the manganese carbonate used as a raw material is not particularly limited, but is characterized in that it is spherical and fine particles.
  • Japanese Patent Application No. 10-370000 Japanese Patent Application No. 10-370000 (Japanese patent) And fine particles characterized by having a spherical shape, a median diameter of 10 m or less, and a tap density of 1.2 g / cm 'or more according to the present invention. It is desirable to apply manganese carbonate.
  • manganese carbonate proposed as Japanese Patent Application No. 10-370000 (Japanese patent application) is composed of divalent manganese ion and carbonate ion or hydrogen carbonate. In the presence of aqueous ammonia.
  • the low-oxidation atmosphere applied in the first-stage heat treatment is to control the oxygen concentration in the atmosphere. Obtained by
  • This low-oxidation manganese oxide has ⁇ , ⁇ , and ⁇ . Is a mixture of ⁇ (mainly ⁇ , ⁇ , at low heat treatment temperatures and at the beginning of heat treatment). The surface was reddish purple and the surface was observed by SEM (Scanning Electron Microscope). Then, as the heat treatment proceeds, the mixed Mn, 0 «changes to ⁇ , ⁇ ,.
  • the oxygen concentration in the heat treatment atmosphere is less than 15% (preferably 10% or less, more preferably 5% or less). This is because if the oxygen concentration in the heat treatment atmosphere is 15% or more, porous ⁇ 2 is generated, and the tap density is reduced.
  • the heat treatment temperature depends on the treatment time, the amount of manganese carbonate to be treated, the performance of the firing furnace, etc., it is appropriate to be in the range of 400 to 800 ° C. If the treatment temperature in the first stage heat treatment is lower than 400 ° C, manganese oxide in a low oxidation state cannot be obtained effectively. As the manganese oxide agglomeration becomes remarkable, irregular shaped grains increase, and a fine, high tap density (more than very high value of 1.2 g / cm ', especially 1.8 g / cm') manganese oxide is obtained. This is because it will not be possible.
  • manganese oxide with a high density is obtained by performing the first-stage heat treatment.
  • the generation of the property ⁇ may be suppressed, there is also a fact that it is not possible to explain this alone because the fact that the evening-up density gradually increases during this process.
  • the mechanism by which the first-stage heat treatment can provide high tap density manganese oxide is not fully understood, but vacancies in manganese oxide after releasing CO and gas from the heat treatment. It is speculated that "the molten" ⁇ , ⁇ , and ⁇ , ⁇ seep into it, which may increase the evening-up density.
  • the oxygen concentration is increased to 15% or more (preferably 20% or more), and the time required for converting Mn, 0 ⁇ to ⁇ , is shortened.
  • the production time of manganese oxide is reduced to a level that is sufficiently satisfactory for practical operation.
  • the processing temperature in the second heat treatment is set to 530 to 800 ° C (preferably 550 to 750 ° C).
  • the oxygen concentration in the heat treatment atmosphere is or less than 1 5% contaminating ⁇ , ⁇ 4 is Myuita, Omicron,
  • the conversion may not be performed quickly, and it may take a long time to process or deteriorate the product performance. If the processing temperature in the second stage heat treatment exceeds 800 ° C, the resulting manganese oxide will also be remarkably agglomerated, resulting in a fine and high tap density (1.2 g / cm s or more, especially 1.8 g / cm 2). cm s or more).
  • the switching of the heat treatment temperature for converting Mn, 0 to Mn, ⁇ may be performed simultaneously with the generation of manganese oxide in a low oxidation state, and the oxygen concentration in the heat treatment atmosphere is not less than 15%. It does not need to be at the point where it was raised.
  • the heat treatment time also depends on the heat treatment temperature, the amount of manganese carbonate to be treated, the performance of the firing furnace, etc., but considering the workability and the characteristics of the obtained manganese oxide, the heat treatment time in the first heat treatment is 0.5. About 10 to 10 hours, and about 0.5 to 10 hours for the second stage heat treatment.
  • the present invention is "median diameter 1 0 m or less or even tap density is 1.8 g / cm s or more spherical lithium 'manganese composite oxide (Li ⁇ ⁇ , represents a 0 J fruit, also this cathode material Has been a problem in the development of lithium-manganese composite oxide-based lithium secondary batteries. It is also characterized by the fact that the cycle characteristics are significantly improved.
  • lithium ⁇ manganese composite oxide according to the present invention (Li x Mn, 0 4) , was a value of X is the ratio of Li to limit the "1.0 ⁇ x ⁇ 1.2", the value of X is 1.0 If it is less than 1.2, the spinel structure becomes unstable, and if it exceeds 1.2, the discharge capacity when it is used as the positive electrode active material of a lithium secondary battery is 100 mAh / g or less. This is not preferable.
  • Lithium-manganese composite oxide (Li Jn! O has a median diameter of 10 m or less and its particle shape is limited to a spherical shape. This is because the first cycle of the lithium-manganese composite oxide shows a good cycle characteristic at 1.8 g / cm s J ⁇ . When the maximum particle size of the composite oxide is suppressed to 20 ⁇ m or less, the improvement is more remarkable.
  • the lithium-manganese composite oxide according to the present invention exhibits good cycle characteristics even at high temperatures when used as a positive electrode active material of a lithium secondary battery is that the composite oxide has a small particle size. Therefore, it is thought that one of the reasons is that the applicability to the electrode is improved because the tap density is high.
  • the particle shape is spherical, the expansion and contraction during the charge / discharge reaction occurs evenly in one direction, so that stress is not easily generated inside the particle during expansion and contraction, and the particle does not easily collapse.
  • Another reason for the improvement of the cycle characteristics is that the contact with the conductive material constituting the electrode is more easily maintained than in the case where the particles are amorphous due to the uniform expansion and contraction. You.
  • Such fine particle lithium ⁇ Manganese composite oxide (Li ⁇ ⁇ , ⁇ J is main-di Ann diameter can be produced by mixing calcined 1 0 m or less manganese oxide (MnO ,, Mn, 0 5 or Mn s 0,) and Lithium compound (lithium carbonate) in a predetermined ratio.
  • the sintering temperature 4 5 0 ⁇ 9 0 0 ° there are appropriate ranges and C
  • the battery because the firing temperature that does not rise crystalline Lijn! O 4 is less than 4 5 0 ° C
  • the temperature exceeds 900 ° C the release of oxygen from Li x Mn, 0, becomes remarkable during firing, and a different phase is generated. It is not preferable because the discharge capacity of the material tends to decrease.
  • the manganese oxide as a firing raw material has a tap density of 1.8 g / cm s or more, more preferably It is better to use one with a spherical particle shape.
  • Manganese oxide (MnO 2 , Mn, 0 ,, ⁇ , ,,) as a firing raw material can be produced by heat-treating fine-grained manganese carbonate at 300 or more in air.
  • a more preferable manganese oxide raw material is a heat treatment of manganese carbonate having a spherical particle shape at 400 to 800 in an atmosphere having an oxygen concentration of less than 15% (first heat treatment). Then, it can be manufactured by further performing a heat treatment (second heat treatment) at 530 to 800 ° C. in an atmosphere having an oxygen concentration of 15% or more.
  • the chemical composition is expressed as LiJn! O 1.0 ⁇ X ⁇ 1.2) and the median diameter is 10 m or less, and the tap density is 1.8 g / cm or more.
  • C 0 gas was blown into the filtrate obtained by filtering the above solution at a blow rate of 2.5 / min.
  • the manganese carbonate was separated by filtration and dried at 105 ° C. for 2 hours to obtain 58 g of fine manganese carbonate.
  • the maximum diameter was 10.1 m and the median diameter was 5.2 m.
  • the tap density of the obtained fine-grained manganese carbonate was measured, the tap density was 1.28 g / cm '.
  • the manganese carbonate was filtered off and dried at 105 ° C. for 2 hours to obtain 120 g of fine-grained manganese carbonate.
  • the maximum particle size was 10.4 m and the median diameter was 4.8 m.
  • the tap density of the obtained fine-grained manganese carbonate was measured, the tap density was 1.28 g / cm '.
  • the manganese carbonate was filtered off and dried at 105 ° C for 2 hours. 75 g of fine-grained manganese carbonate was obtained.
  • the maximum particle size was 8.8 m and the median size was 3.8 ⁇ m.
  • the tap density of the obtained fine-grained manganese carbonate was measured, and the tap density was 1.28 g / cm 3 .
  • C 0 gas was blown into the filtrate obtained by filtering the solution at a blow rate of 2.5 £ / min.
  • the manganese carbonate was separated by filtration and dried at 105 under 2 hours to obtain 31 g of manganese carbonate particles.
  • the particle size and particle size distribution of the obtained manganese carbonate particles were measured using a fine particle analyzer.
  • the maximum particle size was 175 ⁇ m and the median size was 26.m.
  • the tap density of the obtained manganese carbonate particles was measured, the tap density was 0.93 g / cm s .
  • Table 1 shows the metal manganese dissolution conditions in each of the above Examples and Comparative Examples. 5 is a list in which the characteristics of the obtained manganese carbonate particles are compared.
  • the manganese carbonate was filtered off and dried at 105 ° C for 2 hours to obtain 43.5 g of fine-grained manganese carbonate.
  • the particle size and particle size distribution of the obtained fine-grained manganese carbonate were measured using a fine particle analyzer, and the maximum particle size was 11.5 m, and the median size was 11.5 m. Was 2.5 m.
  • the evening density of the obtained fine-grained manganese carbonate was measured, the evening density was 1.25 g / cm '.
  • the manganese carbonate in the liquid was separated by filtration and dried at 105 ° C. for 2 hours to obtain 45.5 g of fine-grained manganese carbonate.
  • the particle size and the particle size distribution of the thus obtained fine manganese carbonate were measured using a fine particle analyzer.
  • the maximum particle size was 20 / m and the median diameter was 6.2 m.
  • the tap density of the obtained fine-grained manganese carbonate was measured, the tap density was 1.30 g / cm '.
  • the shape of the obtained fine manganese carbonate particles was observed using SEM. As a result, it had a shape close to a true sphere.
  • the solution was adjusted to 12 liters of CH, COOH, and the solution having a concentration of 6. Omol / J? Using deionized water.
  • the manganese carbonate thus obtained was separated by filtration and dried at 105 ° C. for 2 hours to obtain 540 g of fine-grained manganese carbonate.
  • the maximum particle size was 30 ⁇ m and the median diameter was 8.0 m. Further, the evening density of the obtained fine-grained manganese carbonate was measured and found to be 1.40 g / cm s .
  • the charged material manganese carbonate powder
  • the oxygen concentration was increased to 21%
  • the heat treatment was continued for another hour at the same temperature. went.
  • the particles had a spherical shape close to a true sphere.
  • Example 7 100 g of the same manganese carbonate powder as in Example 7 (maximum particle size 10.1 4.5m, median diameter 4.5 m, tap density 1.33 g / cm s ) was charged into a stainless steel reaction vessel. Subsequently, a mixed gas of air and nitrogen was passed through the reaction vessel at a flow rate of 500 m £ / min so that the oxygen concentration became 10%.
  • the charge (manganese carbonate powder) was added at 65 ° C for 1 hour. After the heat treatment, the oxygen concentration was increased to 21%, followed by another 1 hour heat treatment at the same temperature.
  • the maximum particle size was 10.1 m
  • the median size was 4.5 m
  • the tap density was 2.06 g / cm s , similar to the raw material. .
  • the charged raw material (manganese carbonate powder) was heat-treated at 65 ° C. for 2 hours.
  • the black compound thus obtained was subjected to powder X-ray diffraction measurement, and was found to be ⁇ , ⁇ and a single phase.
  • the maximum particle size was 10.1 m and the median diameter was 4.5 m as in the case of the raw material.
  • the packing density was 1.19 g / cm s .
  • the charged raw material (manganese carbonate powder) is heated at 65 ° C. Heat treatment was performed for 2 hours.
  • the black compound thus obtained was subjected to powder X-ray diffraction measurement and found to be Mn, 0 and a single phase.
  • the maximum particle size was 10.1 m and the median size was 4.5 ⁇ m as in the case of the raw material.
  • the tap density was 1.10 g / cm s .
  • spherical manganese carbonate having a maximum particle size of 10.1 and a median diameter of 4.5 m was prepared, and calcined at 65 ° C for 1 hour in a 5% oxygen atmosphere. Sintering was further performed at 650 ° C for 1 hour while changing the medium oxygen concentration to 21% to obtain spherical ⁇ ⁇ , 0 with a maximum particle size of 10.1 ⁇ m and a median diameter of 4.6 ⁇ m.
  • the lithium-manganese composite oxide (Li Jn, 0 J particles had a maximum particle size of 10.1 m and a median diameter of 4.6 m.
  • the tap density was 2.15 g / cm s . Atsuta.
  • the obtained lithium-manganese composite oxide (LuMn! O 4 ) was used as an active material at 85 wt%, acetylene black as a conductive material at 8 wt%, and polyether as a binder. 7 wt% of vinylidene fluoride is weighed, and N-methylpyrrolidone is added as a dispersion medium to form a slurry, which is then placed on aluminum foil. Then, the solvent was evaporated to prepare a positive electrode of a lithium battery.
  • a coin cell (CR2032) as a lithium battery was manufactured.
  • a mixed raw material (mixed raw material of fine particles ⁇ , ⁇ and lithium carbonate) under the same conditions as in Example 9 was fired in air at 650 ° C for 10 hours.
  • the powder of the compound thus obtained was subjected to powder X-ray diffraction measurement. As a result, it was confirmed that the compound was a single phase of Li x Mn O (1.0 ⁇ x ⁇ 1.2).
  • the maximum particle diameter of the lithium-manganese composite oxide (Li x Mn, 0 J particles was 10.1 m, the median diameter was 4.5 m.
  • the tap density was 2.13 g / cm '. there were.
  • lithium x Mn! O, lithium'manganese composite oxide
  • Example 9 Manganese composite oxide (Li x Mn, 0 4) was used as a positive electrode active substance, and the other is a lithium battery in the same manner as in Example 9 carp Nseru (CR 2 0 3 2) They were fabricated and their cycle characteristics were examined.
  • Electrolytic manganese dioxide and lithium carbonate were mixed so as to have the same “LiZMn ratio” as the “mixed raw material of fine particles ⁇ , ⁇ , and lithium carbonate” in Example 9, and this was mixed at 680 ° C. in air. For 10 hours.
  • the obtained powder of the compound was measured powder X-ray diffraction, it was confirmed that a Li x Mn 2 0 4 single phase (1.0 ⁇ x ⁇ 1.2).
  • the maximum particle size of the lithium-manganese composite oxide (Li x Mn, 0 J particles was 1 16 ⁇ m and the median size was 22.3 m.
  • the tap density was 2.15 g / cm '. Met.
  • the present invention it is possible to stably provide spherical fine-grained manganese carbonate having a median diameter of 10 m or less and a tap density of 1.2 g / cm 'or more. It is possible to manufacture manganese dioxide for manganese primary batteries and lithium-manganese composite oxides (Li x Mn, 0J) for lithium secondary batteries with satisfactory battery characteristics.
  • an oxide mask having a high tap density even with a small particle size is provided. It is also possible to provide a stable supply of lithium manganese composite oxide (LiJn, 0,) for lithium secondary batteries with sufficiently satisfactory battery characteristics by using this as a raw material. Becomes possible.
  • lithium-manganese composite oxide (LixMn! OJ), which is fine particles and has a high tap density, more stably, and has excellent battery characteristics.
  • Industrially extremely useful effects such as the realization of a relatively inexpensive “lithium battery using a lithium-manganese composite oxide as a positive electrode active material” can be realized.

Abstract

L'invention porte sur un procédé de préparation d'un carbonate de manganèse particulaire sphérique dont le diamètre médian est égal ou inférieur à 10 νm et la densité après tassement est égale ou supérieure à 1,2 g/cm3. Ce procédé consiste à dissoudre un manganèse métallique dans une solution ionique d'ammonium et insuffler un gaz CO¿2? dans la solution obtenue dans une plage spécifique du pH. L'invention porte également sur un procédé de préparation d'un oxyde de manganèse particulaire dont le diamètre médian est égal ou inférieur à 10 νm et la densité après tassement est égale ou supérieure à 1,8 g/cm?3¿. Ce procédé consiste à soumettre le carbonate de manganèse à un premier traitement thermique dans une atmosphère à forte concentration en oxygène. On obtient un oxyde double de lithium-manganèse particulaire, sphérique et de densité élevée, en brûlant l'oxyde de manganèse précité avec un composé de lithium, et on obtient une pile secondaire au lithium aux performances élevées en utilisant l'oxyde double de lithium-manganèse comme matériau actif d'une électrode positive. L'invention porte sur un carbonate de manganèse et un oxyde double de lithium-manganèse qui sont appropriés pour être utilisés comme matériaux dans la fabrication d'une pile, ainsi que sur une pile secondaire au lithium les utilisant et présentant des caractéristiques supérieures.
PCT/JP2000/001856 1999-03-29 2000-03-27 Compose de manganese particulaire et son procede de preparation, et cellule secondaire utilisant ce compose WO2000058221A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP08511499A JP3495639B2 (ja) 1999-03-29 1999-03-29 リチウム・マンガン複合酸化物とその製造法並びに該複合酸化物を使用したリチウム二次電池
JP11/85093 1999-03-29
JP11/85106 1999-03-29
JP11085093A JP2000281347A (ja) 1999-03-29 1999-03-29 微細粒炭酸マンガン及びその製造方法
JP08510699A JP3495638B2 (ja) 1999-03-29 1999-03-29 リチウム二次電池用微細粒三酸化二マンガン及びその製造方法
JP11/85114 1999-03-29
JP2000/43588 2000-02-16
JP2000043588A JP3495676B2 (ja) 2000-02-16 2000-02-16 微細粒炭酸マンガン及びその製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110282665A (zh) * 2019-07-04 2019-09-27 成都尤尼瑞克科技有限公司 一种具有介观结构的锂电池正极材料前驱体及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57200229A (en) * 1981-06-04 1982-12-08 Chuo Denki Kogyo Kk Preparation of high-density manganese carbonate
JPS59146943A (ja) * 1983-02-14 1984-08-23 Toho Aen Kk 充填密度の大きい炭酸マンガンの製造方法
JPH02145429A (ja) * 1988-11-25 1990-06-04 Chuo Denki Kogyo Kk 乾電池用マンガン酸化物及びその製造方法
JPH02145435A (ja) * 1988-11-25 1990-06-04 Chuo Denki Kogyo Kk 高密度化成二酸化マンガンとその製造方法
JPH08208231A (ja) * 1995-01-26 1996-08-13 Japan Metals & Chem Co Ltd スピネル型 ＬｉＭｎ２Ｏ４の製造方法
JPH08236112A (ja) * 1995-02-24 1996-09-13 Aichi Steel Works Ltd リチウム二次電池用粉末状活物質の製造方法
JPH09320603A (ja) * 1996-03-28 1997-12-12 Aichi Steel Works Ltd リチウム二次電池用粉末状活物質の製造方法
JPH10172567A (ja) * 1996-12-17 1998-06-26 Nikki Kagaku Kk マンガン酸リチウムの製法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57200229A (en) * 1981-06-04 1982-12-08 Chuo Denki Kogyo Kk Preparation of high-density manganese carbonate
JPS59146943A (ja) * 1983-02-14 1984-08-23 Toho Aen Kk 充填密度の大きい炭酸マンガンの製造方法
JPH02145429A (ja) * 1988-11-25 1990-06-04 Chuo Denki Kogyo Kk 乾電池用マンガン酸化物及びその製造方法
JPH02145435A (ja) * 1988-11-25 1990-06-04 Chuo Denki Kogyo Kk 高密度化成二酸化マンガンとその製造方法
JPH08208231A (ja) * 1995-01-26 1996-08-13 Japan Metals & Chem Co Ltd スピネル型 ＬｉＭｎ２Ｏ４の製造方法
JPH08236112A (ja) * 1995-02-24 1996-09-13 Aichi Steel Works Ltd リチウム二次電池用粉末状活物質の製造方法
JPH09320603A (ja) * 1996-03-28 1997-12-12 Aichi Steel Works Ltd リチウム二次電池用粉末状活物質の製造方法
JPH10172567A (ja) * 1996-12-17 1998-06-26 Nikki Kagaku Kk マンガン酸リチウムの製法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110282665A (zh) * 2019-07-04 2019-09-27 成都尤尼瑞克科技有限公司 一种具有介观结构的锂电池正极材料前驱体及其制备方法

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