WO2011002074A1 - Procédé de fabrication d'un oxyde de lithium et de métal de transition - Google Patents

Procédé de fabrication d'un oxyde de lithium et de métal de transition Download PDF

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WO2011002074A1
WO2011002074A1 PCT/JP2010/061308 JP2010061308W WO2011002074A1 WO 2011002074 A1 WO2011002074 A1 WO 2011002074A1 JP 2010061308 W JP2010061308 W JP 2010061308W WO 2011002074 A1 WO2011002074 A1 WO 2011002074A1
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transition metal
metal oxide
lithium transition
temperature
oxygen
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PCT/JP2010/061308
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English (en)
Japanese (ja)
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蔭井　慎也
啓祐 宮之原
祥巳 畑
越智　康弘
徹也 光本
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三井金属鉱業株式会社
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Priority to JP2010545129A priority Critical patent/JP4673451B2/ja
Publication of WO2011002074A1 publication Critical patent/WO2011002074A1/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
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • 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
    • C01P2006/40—Electric properties
    • 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 method for producing a lithium transition metal oxide, particularly a lithium transition metal oxide that can be used as a positive electrode active material of a lithium secondary battery.
  • Lithium batteries especially lithium secondary batteries, have features such as high energy density and long life, and power supplies for home appliances such as video cameras, portable electronic devices such as notebook computers and mobile phones. Is widely used. Recently, application to large batteries mounted on electric vehicles (EV), hybrid electric vehicles (HEV), and the like is expected.
  • EV electric vehicles
  • HEV hybrid electric vehicles
  • a lithium secondary battery is a secondary battery with a structure in which lithium is extracted as ions from the positive electrode during charging, moves to the negative electrode and is stored, and reversely, lithium ions return from the negative electrode to the positive electrode during discharging. It is known to be due to the potential of the material.
  • lithium transition metal oxides such as LiCoO 2 , LiNiO 2 , and LiMnO 2 having a layer structure, LiMn 2 O 4 , and LiNi 0.5 Mn.
  • a lithium transition metal oxide having a manganese-based spinel structure (Fd-3m) such as 1.5 O 4 (also referred to as “spinel-type lithium transition metal oxide” or “LMO” in the present invention) is known.
  • Manganese spinel-type lithium transition metal oxide is a positive electrode for large batteries such as electric vehicles (EV) and hybrid electric vehicles (HEV) because of its low raw material price, non-toxicity, and high safety. It is attracting attention as an active material. Moreover, excellent output characteristics are particularly required for batteries for EVs and HEVs. In this regard, insertion and desorption of Li ions are three-dimensionally compared with lithium transition metal oxides such as LiCoO 2 having a layer structure. A possible spinel type lithium transition metal oxide (LMO) has excellent output characteristics.
  • LMO lithium transition metal oxide
  • Patent Document 1 discloses a method of suppressing oxygen deficiency by adding lithium hydroxide after high-temperature baking and re-baking at a lower temperature.
  • the starting material is baked in an oxidizing atmosphere at a temperature in the range of 900 to 1000 ° C. for 5 to 50 hours, and then in an oxidizing atmosphere at 600 to 900 ° C.
  • a method for suppressing oxygen deficiency by re-baking at a temperature in the range of 1 to 50 hours for a time in the range of 1 to 50 hours is disclosed.
  • Patent Document 3 proposes a method for producing a lithium composite oxide in which a mixture of raw materials is fired at a high temperature to produce a fired product, and the fired product is refired while flowing.
  • the present invention provides a method for producing a lithium transition metal oxide comprising a step of mixing raw materials, a step of firing, and a step of heat treatment, in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa. And heat treatment at a primary oxygen release temperature of ⁇ 50 ° C. in an atmosphere having an oxygen partial pressure of 0.03 MPa or more after baking at 850 ° C. in a method for producing a lithium transition metal oxide This is a proposal.
  • the crystallite size can be increased and the distortion of the crystal structure can be suppressed, the distortion is reduced and the skeleton is strengthened.
  • a positive electrode active material of a lithium secondary battery When used, it is possible to provide a new lithium transition metal oxide capable of achieving both output characteristics (rate characteristics) and high-temperature cycle life characteristics.
  • the manufacturing method of the present invention it is possible to suppress the distortion of the crystal structure while increasing the crystallite size as described above, the strain is 0.05 or less, and the crystallite size is 250 nm to A 1000 nm spinel lithium transition metal oxide can be obtained.
  • Such spinel-type lithium transition metal oxides are not recognized as publicly known in Japan at the time of this application.
  • FIG. It is the figure which showed the structure of the cell for electrochemical produced in order to evaluate the battery characteristic of the sample obtained by the Example and the comparative example.
  • This embodiment relates to a method for producing a spinel (Fd-3m) lithium transition metal oxide.
  • the manufacturing method of this embodiment is characterized in that after the raw materials are mixed, calcined at 850 ° C. or higher in a predetermined oxygen partial pressure atmosphere, and then heat-treated in an atmosphere having a higher oxygen partial pressure than the atmosphere. .
  • the details will be described in order.
  • At least a lithium material and a manganese material may be appropriately selected.
  • the lithium raw material is not particularly limited.
  • lithium hydroxide LiOH
  • lithium carbonate Li 2 CO 3
  • lithium nitrate LiNO 3
  • LiOH.H 2 O LiOH.H 2 O
  • lithium oxide Li 2 O
  • lithium hydroxide salts carbonates and nitrates are preferred.
  • manganese raw material any of manganese dioxide, trimanganese tetroxide, dimanganese trioxide, manganese carbonate, or a mixture of two or more selected from these can be used.
  • manganese dioxide chemically synthesized manganese dioxide (CMD), electrolytic manganese dioxide (EMD) obtained by electrolysis, manganese carbonate, or natural manganese dioxide can be used.
  • a magnesium raw material in addition to the lithium raw material and the manganese raw material, for example, a magnesium raw material, an aluminum raw material, and other substances known as starting materials for lithium transition metal oxides can be blended.
  • the magnesium raw material is not particularly limited.
  • the aluminum raw material is not particularly limited.
  • aluminum hydroxide (Al (OH) 3 ), aluminum fluoride (AlF 3 ), or the like can be used, and aluminum hydroxide is particularly preferable.
  • Examples of other substances known as starting materials for lithium transition metal oxides include elements such as Ti, Ni, Co and Fe, and the starting materials are not particularly limited.
  • an oxide or hydroxide may be blended.
  • the method of mixing raw materials is not particularly limited as long as it can be uniformly mixed.
  • the respective raw materials may be added simultaneously or in an appropriate order using a known mixer such as a mixer, and mixed by stirring in a wet or dry manner.
  • a known mixer such as a mixer
  • wet mixing When adding an element that is difficult to replace, such as aluminum, it is preferable to employ wet mixing.
  • Examples of the dry mixing include a mixing method using a precision mixer that rotates mixed powder at a high speed.
  • examples of the wet mixing include a mixing method in which a liquid medium such as water or a dispersant is added and wet mixed to form a slurry, and the resulting slurry is pulverized with a wet pulverizer. It is particularly preferable to grind to submicron order. After pulverizing to the submicron order, granulation and baking can increase the uniformity of each particle before the baking reaction, and the reactivity can be increased.
  • the raw materials mixed as described above may be granulated to a predetermined size, if necessary, and then fired. However, granulation is not necessarily performed.
  • the granulation method may be wet or dry as long as the various raw materials pulverized in the previous step are dispersed in the granulated particles without being separated, and the extrusion granulation method, rolling granulation method, fluidized granulation method, A mixed granulation method, a spray drying granulation method, a pressure molding granulation method, or a flake granulation method using a roll or the like may be used. However, when wet granulation is performed, it is necessary to sufficiently dry before firing.
  • a drying method it may be dried by a known drying method such as a spray heat drying method, a hot air drying method, a vacuum drying method, a freeze drying method, etc.
  • the spray heat drying method is preferable.
  • the spray heat drying method is preferably performed using a heat spray dryer (spray dryer).
  • a thermal spray dryer spray dryer
  • the particle size distribution can be made sharper, and the secondary particles can be formed so as to contain agglomerated particles (secondary particles) formed by agglomeration. Forms can be prepared.
  • (Baking) Firing is preferably performed in an atmosphere having an oxygen partial pressure of 0.015 MPa to 0.15 MPa, for example, in an air atmosphere. If the oxygen partial pressure is higher than 0.15 MPa, crystal growth cannot be promoted and the crystallite size cannot be increased. In addition, as will be described later, in order to promote crystal growth by firing, it is preferable that the oxygen partial pressure in the atmosphere is low. However, if the oxygen partial pressure during firing is too low, oxygen deficiency will increase and heat treatment will also occur. Since the strain cannot be recovered, baking is preferably performed at an oxygen partial pressure of 0.015 MPa or more. From this point of view, the oxygen partial pressure during firing is more preferably 0.015 MPa to 0.13 MPa, particularly 0.015 MPa to 0.12 MPa, especially 0.015 MPa or more, or less than 0.08 MPa. preferable.
  • the firing temperature can be increased at 850 ° C. or more, particularly 910 to 1,050 ° C., particularly 910 to 980 ° C., because high temperature firing can promote crystal growth and increase the crystallite size. preferable.
  • the firing temperature means the product temperature of the fired product measured by bringing a thermocouple into contact with the fired product in the firing furnace.
  • the firing time that is, the time for maintaining the firing temperature may be 0.5 to 30 hours, although it depends on the firing temperature.
  • the type of firing furnace is not particularly limited. For example, it can be fired using a rotary kiln, a stationary furnace, or other firing furnace.
  • Heat treatment Next, it is important to perform heat treatment at a temperature of primary oxygen release temperature ⁇ 50 ° C. in an atmosphere having an oxygen partial pressure higher than that of air. By performing the heat treatment in this manner, crystal distortion can be reduced.
  • the atmosphere for the heat treatment is preferably such that the oxygen partial pressure is 0.03 MPa or higher and the oxygen partial pressure is higher than that during firing, particularly 0.05 MPa or higher, particularly 0.08 MPa or higher.
  • the pressure of the atmosphere during the heat treatment is preferably controlled to a pressure higher than atmospheric pressure, for example, 0.1 MPa to 1.5 MPa.
  • a pressure higher than atmospheric pressure for example, 0.1 MPa to 1.5 MPa.
  • the pressure of the atmosphere during the heat treatment is preferably controlled to 0.1 MPa to 1.5 MPa, more preferably 0.1 MPa to 1.3 MPa, and particularly preferably 0.1 MPa to 1.0 MPa.
  • the heat treatment preferably maintains the primary oxygen release temperature ⁇ 50 ° C., particularly ⁇ 35 ° C., especially ⁇ 30 ° C., and especially ⁇ 20 ° C. Among these, it is more preferable to maintain a temperature range higher than the primary oxygen release temperature in each of the above temperature ranges from the viewpoint that energy exceeding the primary oxygen release temperature can be given.
  • the temperature of this heat treatment means the product temperature of the processed material measured by bringing a thermocouple into contact with the processed material in the furnace.
  • the rate of temperature rise is preferably 0.5 ° C./min to 4 ° C./min, particularly 0.5 ° C./min to 3 ° C./min, and particularly 0.5 ° C./min to 2 ° C./min More preferably, it is set to min.
  • the primary oxygen release temperature can be obtained as the starting temperature at which the spinel-type lithium transition metal oxide after heating is heated and the weight is reduced in the range of 600 ° C. to 900 ° C. (see FIG. 1).
  • the time for maintaining the primary oxygen release temperature ⁇ 50 ° C. in the heat treatment needs to be at least 1 minute. In order to fully incorporate oxygen into the crystal structure, at least one minute is considered necessary. From this viewpoint, the time for maintaining the primary oxygen release temperature ⁇ 50 ° C. is preferably 5 minutes or more, particularly preferably 10 minutes or more.
  • the temperature lowering rate after the heat treatment is preferably slow cooling at a cooling rate of 10 ° C./min or less to at least 500 ° C., particularly 0.1 ° C./min to 8 ° C./min, especially 0.5 ° C./min to More preferably, it is controlled to 5 ° C./min. Since the oxygen taken in near the primary oxygen release temperature is considered to be stabilized, the oxygen is slowly cooled at a temperature lowering rate of 10 ° C./min or less until the temperature close to the primary oxygen release temperature, that is, at least 500 ° C. Can be considered preferable.
  • Lithium transition metal oxide According to the manufacturing method of the present embodiment described above, a spinel type lithium transition metal oxide (also referred to as “present LMO”) having the characteristics described below can be obtained.
  • the present LMO is a spinel (Fd-3m) lithium transition metal oxide containing, in addition to Li and Mn, any one of Ti, Ni, Mg, Co and Fe, or a combination of two or more thereof.
  • the content of substitutional elements other than Li and Mn is preferably 0 to 1.8 wt%, particularly 0.2 to 1.0 wt%, particularly 0.4 to 0.6 wt% from the viewpoint of strain removal. Is even more preferable.
  • the strain of the obtained spinel-type lithium transition metal oxide can be adjusted to 0.05 or less, preferably 0.02 or less, and more preferably 0.009 or less.
  • the skeleton of the spinel lithium transition metal oxide becomes stronger, and when used as a positive electrode active material for a lithium secondary battery, the output characteristics (rate characteristics) and high-temperature cycle life characteristics It can be compatible.
  • the spinel-type lithium transition metal oxide obtained has a crystallite size of 250 nm to 1000 nm, particularly 300 to 1000 nm, preferably 350 nm to 900 nm, and particularly preferably 420 nm to 750 nm. Can be adjusted.
  • the crystallite size of the present LMO By setting the crystallite size of the present LMO to 250 nm to 1000 nm, the high temperature cycle life characteristics can be improved, and both the output characteristics and the high temperature cycle life characteristics can be achieved.
  • crystallite means the largest group that can be regarded as a single crystal, and can be obtained by XRD measurement and Rietveld analysis.
  • the present LMO can be effectively used as a positive electrode active material of a lithium battery after being crushed and classified as necessary.
  • the positive electrode mixture can be manufactured by mixing the present LMO, a conductive material made of carbon black or the like, and a binder made of Teflon (registered trademark) binder or the like.
  • a positive electrode mixture is used for the positive electrode, for example, a material that can occlude / desorb lithium such as lithium or carbon is used for the negative electrode, and a lithium salt such as lithium hexafluorophosphate (LiPF6) is used for the non-aqueous electrolyte.
  • a lithium secondary battery can be formed by using a material in which is dissolved in a mixed solvent such as ethylene carbonate-dimethyl carbonate.
  • the present invention is not limited to the battery having such a configuration.
  • a lithium battery equipped with the LMO as a positive electrode active material has both excellent life characteristics (cycle life characteristics) and output characteristics when repeatedly used in charge and discharge in the central region of the charge / discharge depth (eg, SOC 50-80%). Since it exhibits, it is particularly excellent in the use of a positive electrode active material of a large-sized lithium battery used as a power source for driving a motor mounted on an electric vehicle (EV) or a hybrid electric vehicle (HEV).
  • EV electric vehicle
  • HEV hybrid electric vehicle
  • HEV means an automobile using two power sources, that is, an electric motor and an internal combustion engine.
  • lithium battery is intended to encompass all batteries containing lithium or lithium ions in the battery, such as lithium primary batteries, lithium secondary batteries, lithium ion secondary batteries, and lithium polymer batteries.
  • X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
  • X or more is an arbitrary number
  • Y or less is an arbitrary number
  • the Rietveld method using the fundamental method is a method for refining the crystal structure parameters from the diffraction intensity obtained by powder X-ray diffraction or the like. This method assumes a crystal structure model, and refines various parameters of the crystal structure so that the X-ray diffraction pattern derived from the structure and the measured X-ray diffraction pattern match as much as possible.
  • Detector PSD Detector Type: VANTEC-1 High Voltage: 5616V Discr. Lower Level: 0.35V Discr. Window Width: 0.15V Grid Lower Level: 0.075V Grid Window Width: 0.524V Flood Field Correction: Disabled Primary radius: 250mm Secondary radius: 250mm Receiving slit width: 0.1436626mm Divergence angle: 0.3 ° Filament Length: 12mm Sample Length: 25mm Receiving Slit Length: 12mm Primary Sollers: 2.623 ° Secondary Sollers: 2.623 ° Lorentzian, 1 / Cos: 0.01630098Th
  • Li battery evaluation was performed by the following method.
  • PVDF Korean Chemical Co., Ltd.
  • positive electrode active material spinel type lithium transition metal oxide obtained in Examples and Comparative Examples
  • 0.60 g of acetylene black manufactured by Denki Kagaku Kogyo
  • NMP N-methylpyrrolidone
  • 5.0 g of 12 wt% dissolved solution was accurately weighed and 5 ml of NMP was added and mixed well to prepare a paste.
  • This paste is placed on an aluminum foil as a current collector, formed into a coating film with an applicator adjusted to a gap of 250 ⁇ m, vacuum-dried at 120 ° C.
  • the negative electrode was made of metal Li having a diameter of 20 mm and a thickness of 1.0 mm, and an electrochemical evaluation cell TOMCEL (registered trademark) shown in FIG. 2 was produced using these materials.
  • the positive electrode 3 made of the positive electrode mixture was disposed at the inner center of the lower body 1 made of organic electrolyte-resistant stainless steel.
  • a separator 4 made of a microporous polypropylene resin impregnated with an electrolytic solution was disposed, and the separator was fixed with a Teflon (registered trademark) spacer 5.
  • a negative electrode 6 made of metal Li was disposed below, a spacer 7 also serving as a negative electrode terminal was disposed, and the upper body 2 was placed thereon and tightened with screws to seal the battery.
  • the electrolytic solution used was a mixture of EC and DMC in a volume of 3: 7, and a solvent in which LiPF 6 was dissolved in 1 mol / L as a solute.
  • the high temperature cycle life characteristic value (0.1 C) was obtained by dividing the percentage (%) of the numerical value obtained by dividing the discharge capacity at the 50th cycle by the discharge capacity at the second cycle.
  • the same cycle condition was changed from 0.1 C to 1.0 C, and a high temperature cycle life characteristic value (1.0 C) was obtained. All are shown in Table 2 as relative values when the value of Example 3 is taken as 100.
  • Example 1-3 Lithium carbonate 1770.9 g, electrolytic manganese dioxide 7500 g, magnesium oxide 65.7 g were set at a high speed blade rotation speed 400 rpm cross screw with a precision mixer (vertical granulator (Fuji Sangyo Co., Ltd. (FM-VG-25)), Mix for 5 minutes.
  • the fired powder obtained by firing was crushed in a mortar, classified with a sieve having an opening of 53 ⁇ m, and the powder under the sieve was collected to obtain a crushed sample.
  • the obtained crushed sample was heat-treated using a tube furnace heating device (Koyo Thermo System Co., Ltd.). That is, 200 g of crushed samples were filled in a magnetic boat, and this magnetic boat was installed near the center of the tube furnace. Then, while flowing oxygen gas (oxygen concentration 100%) into the tube furnace at a flow rate of 0.5 l / min, the sample was heated to the set temperature shown in Table 1 at a heating rate of 1.7 ° C./min. Hold for a predetermined time. Then, while continuing oxygen inflow, it cooled to room temperature at the temperature-fall rate shown in Table 1, and obtained the spinel type lithium transition metal oxide (sample).
  • the oxygen concentration was measured using an oxygen concentration meter (XPO-318 (New Cosmos Electric Co., Ltd.)) (the same applies to comparative examples described later).
  • the temperature at the time of the firing and the heat treatment is the product temperature of the processed product measured by bringing a thermocouple into contact with the processed product in the furnace (the same applies to comparative examples described later).
  • Example 1 A spinel-type lithium transition metal oxide (sample) was obtained using the same raw materials as in Example 1 except that heat treatment was not performed, and mixing, firing, crushing, and classification were performed in the same manner as in Example 1.
  • Example 2 Using the same raw materials as in Example 1, mixing, firing, crushing and classification were performed in the same manner as in Example 1 to obtain a crushed sample. Next, the obtained crushed sample was heat-treated using a stationary electric furnace. That is, 200 g of the crushed sample was filled in a magnetic boat and shown in Table 1 at a temperature increase rate of 1.7 ° C./min in an air atmosphere (atmospheric pressure: 0.10 MPa, oxygen partial pressure: 0.021 MPa). Heated to the set temperature and held for a predetermined time after reaching. Then, while continuing oxygen inflow, it cooled to room temperature at the temperature-fall rate shown in Table 1, and obtained the spinel type lithium transition metal oxide (sample).
  • Example 4-9 Using the same raw materials as in Example 1, except for changing the atmosphere and heat treatment time in the heat treatment to the conditions shown in Table 3, the mixing of the raw materials to the heat treatment was performed in the same manner as in Example 1 to perform the spinel lithium transition. A metal oxide (sample) was obtained.
  • Examples 10-22 and Comparative Example 4> Using the same raw materials as in Example 1, except that the conditions at the time of firing and heat treatment were changed to the conditions shown in Table 3, the process from mixing of raw materials to heat treatment was carried out in the same manner as in Example 1 to spinel lithium transition A metal oxide (sample) was obtained.
  • Example 23 and Comparative Example 5 Example 1 except that the blending composition of the raw materials was changed to 1770.9 g of lithium carbonate, 7500 g of electrolytic manganese dioxide, and 129.0 g of titanium oxide, and the conditions at the time of firing and heat treatment were changed to the conditions shown in Table 3.
  • the spinel type lithium transition metal oxide (sample) was obtained by carrying out from the mixing of the raw materials to the heat treatment in the same manner as described above.
  • Example 24 The raw material composition was changed to 1770.9 g of lithium carbonate, 7500 g of electrolytic manganese dioxide, 32.87 g of magnesium oxide, and 64.48 g of titanium oxide, and the conditions during firing and heat treatment were changed to the conditions shown in Table 3.
  • the spinel type lithium transition metal oxide was obtained by carrying out from the mixing of the raw materials to the heat treatment in the same manner as in Example 1.
  • Example 25 Except for changing the composition of the raw materials to 1770.9 g of lithium carbonate, 7500 g of electrolytic manganese dioxide, 146.68 g of nickel hydroxide, and changing the conditions at the time of firing and heat treatment to the conditions shown in Table 3, Examples The spinel type lithium transition metal oxide (sample) was obtained by carrying out from the mixing of the raw materials to the heat treatment in the same manner as in 1.
  • Example 26 The raw material composition was changed to lithium carbonate 1770.9 g, electrolytic manganese dioxide 7500 g, cobalt oxyhydroxide 145.48 g, and the conditions at the time of firing and heat treatment were changed to the conditions shown in Table 3
  • the spinel type lithium transition metal oxide (sample) was obtained by carrying out from the mixing of the raw materials to the heat treatment in the same manner as in Example 1.
  • Example 27 The raw material composition was changed to lithium carbonate 1770.9 g, electrolytic manganese dioxide 7500 g, iron (iii) 132.99 g, and the conditions during firing and heat treatment were changed to the conditions shown in Table 3, In the same manner as in Example 1, mixing of raw materials to heat treatment was performed to obtain a spinel type lithium transition metal oxide (sample).
  • Example 28> Except for changing the composition of the raw materials to 1756.3 g of lithium carbonate, 7500 g of electrolytic manganese dioxide, 61.83 g of aluminum hydroxide, and changing the conditions at the time of firing and heat treatment to the conditions shown in Table 3, Example The spinel type lithium transition metal oxide (sample) was obtained by carrying out from the mixing of the raw materials to the heat treatment in the same manner as in 1.
  • the reaction to be heated to around 900 ° C. is a reaction in which particles are grown while releasing oxygen at the primary oxygen release temperature, the secondary oxygen release temperature, and the like.
  • the secondary oxygen release temperature and the secondary oxygen release temperature shift to the high temperature side. As a result, it can be considered that the crystal growth reaction does not proceed and the crystallite size is reduced.
  • the lower the oxygen partial pressure the more the particle growth can be promoted. From this point of view, it is necessary to be 0.15 MPa or less in order to grow particles to the same extent as in the examples. Moreover, if it is about 0.015 Mpa, it can be considered that distortion can be recovered to about the level of the embodiment by heat treatment.
  • the firing temperature at the time of firing it can be considered from the examples and past experience that particles of 850 ° C. or higher can be sufficiently grown. In addition, since firing at a high temperature exceeding 1050 ° C. may cause phase separation in terms of crystal structure, firing at 1050 ° C. or less is preferable.
  • the oxygen partial pressure in the heat treatment is higher than that in the atmosphere (0.021 MPa), particularly an oxygen content of 0.03 MPa or more, from the viewpoint of recovering strain by incorporating oxygen into the crystal structure from Example 1-22. It is considered preferable to perform the heat treatment under pressure. In addition, it can be considered that it is preferable that the oxygen partial pressure is higher than that at the time of firing as compared with the atmosphere at the time of firing.
  • the heating temperature in the heat treatment is heated to the vicinity of the primary oxygen release temperature at which oxygen can easily be taken in, specifically, to the primary oxygen release temperature ⁇ 50 ° C.
  • the primary oxygen release temperature to the primary oxygen release temperature + 50 ° C., that is, higher than the primary oxygen release temperature.
  • heat treatment is preferably performed in the temperature range on the side. From the results of the examples, regarding the pressure of the atmosphere at the time of heat treatment, it can be considered that oxygen of 0.10 MPa or more is more preferable because it is easier to take in oxygen. 5 MPa or less.
  • oxygen taken in the vicinity of the primary oxygen release temperature is stabilized, so that it slowly passes 10 ° C./min or less until the temperature close to the primary oxygen release temperature, that is, at least up to 500 ° C. It is considered preferable to cool at a temperature drop rate.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Compounds Of Iron (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention porte sur un nouveau procédé de fabrication d'un oxyde de lithium et de métal de transition, qui est capable d'augmenter la dimension des cristallites, tout en diminuant les défauts d'oxygène. De façon spécifique, l'invention porte sur un procédé de fabrication d'un oxyde de lithium et de métal de transition, qui comprend une étape de mélange des matières de départ, une étape de cuisson et une étape de traitement thermique, et qui est caractérisée par le fait que les matières de départ sont soumises à une cuisson dans une atmosphère ayant une pression partielle d'oxygène de 0,015 MPa à 0,15 MPa à une température non inférieure à 850°C, puis la matière résultante est traitée par la chaleur dans une atmosphère ayant une pression partielle d'oxygène de pas moins de 0,03 MPa à une température est qui est la température de libération d'oxygène primaire ± 50°C. Étant donné que le procédé est capable de diminuer les défauts d'oxygène tout en augmentant la dimension des cristallites, la contrainte est réduite et l'oxyde de lithium et de métal de transition a un squelette résistant. En conséquence, lorsque l'oxyde de lithium et de métal de transition est utilisé comme matière active d'électrode positive pour une batterie secondaire en lithium, la batterie secondaire en lithium est susceptible de présenter en même temps des caractéristiques de puissance suffisantes et des caractéristiques de durée de vie de cycle à haute température suffisante.
PCT/JP2010/061308 2009-07-03 2010-07-02 Procédé de fabrication d'un oxyde de lithium et de métal de transition WO2011002074A1 (fr)

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WO2012118117A1 (fr) * 2011-03-02 2012-09-07 三井金属鉱業株式会社 Oxyde composite à base de manganèse lithié à structure spinelle
JP2013112531A (ja) * 2011-11-25 2013-06-10 Tanaka Chemical Corp リチウム金属複合酸化物及びその製造方法
US10300560B2 (en) 2013-11-25 2019-05-28 Voestalpine Precision Strip Gmbh Method for producing a preliminary material for a machining tool, and corresponding preliminary material

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US10300560B2 (en) 2013-11-25 2019-05-28 Voestalpine Precision Strip Gmbh Method for producing a preliminary material for a machining tool, and corresponding preliminary material

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