WO2012127796A1 - Procédé pour la production d'oxyde composite contenant du lithium, matériau actif d'électrode positive et batterie secondaire - Google Patents

Procédé pour la production d'oxyde composite contenant du lithium, matériau actif d'électrode positive et batterie secondaire Download PDF

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WO2012127796A1
WO2012127796A1 PCT/JP2012/001528 JP2012001528W WO2012127796A1 WO 2012127796 A1 WO2012127796 A1 WO 2012127796A1 JP 2012001528 W JP2012001528 W JP 2012001528W WO 2012127796 A1 WO2012127796 A1 WO 2012127796A1
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lithium
raw material
molten salt
composite oxide
metal
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English (en)
Japanese (ja)
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雄太 中川
直人 安田
阿部　徹
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株式会社豊田自動織機
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Priority to JP2013505795A priority Critical patent/JP5641132B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0027—Mixed oxides or hydroxides containing one alkali metal
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • 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
    • C01P2002/50—Solid solutions
    • 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
    • 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 composite oxide mainly used as a positive electrode material of a lithium ion secondary battery and a secondary battery using the composite oxide.
  • a lithium ion secondary battery has an active material capable of inserting and removing lithium (Li) in each of a positive electrode and a negative electrode. Then, it operates by moving Li ions in the electrolyte provided between both electrodes.
  • the performance of the lithium ion secondary battery depends on the materials of the positive electrode, the negative electrode and the electrolyte that constitute the secondary battery. Among them, research and development of active material materials forming active materials are being actively conducted.
  • lithium-containing as a positive electrode active material of a lithium ion secondary battery comprising lithium and another metal element having a layered rock salt structure of LiCoO 2, LiNiO 2, Li 2 MnO 3, ⁇ -NaFeO 2 type, such as LiFeO 2 Complex oxides are known.
  • Li 2 MnO 3 when using the secondary battery containing Li 2 MnO 3 as a positive electrode active material, it is necessary to activate the positive electrode active material prior to use.
  • the particle size of Li 2 MnO 3 when the particle size of Li 2 MnO 3 is large, only the surface layer of the particles is activated. It is considered necessary to reduce the particle size of Li 2 MnO 3 in order to make almost the entire amount of Li 2 MnO 3 used as a material active as a battery.
  • Patent Document 1 discloses a method for synthesizing nano-order oxide particles.
  • a molten salt raw material in which LiOH ⁇ H 2 O and LiNO 3 are mixed at a molar ratio of 1: 1 and drying 300 Fine particles of various lithium-containing composite oxides are synthesized using the molten salt that has been cooled to ° C.
  • Example 1 of Patent Document 2 the Mn 2 O 3 powder is reacted in a molten salt in which a LiOH ⁇ H 2 O powder is set to 600 ° C. in a nickel crucible, and the average oxidation number of manganese is trivalent. A fine powder of orthorhombic o-LiMnO 2 is obtained.
  • water derived from hydration water is present in the molten salt obtained by heating lithium hydroxide monohydrate.
  • the water may boil and the molten salt may scatter.
  • the water present in the molten salt containing lithium hydroxide has a very high pH.
  • the nickel dissolves from the crucible. That is, there is a possibility that nickel may be mixed as an impurity in the lithium manganese-based composite oxide obtained in the present embodiment.
  • the presence of high pH water also affects the structure of the resulting complex oxide.
  • Patent Document 1 the use of the lithium hydroxide monohydrate as a raw material of the molten salt, and then dried by addition of Li 2 O 2 before melting. This drying is performed for the purpose of increasing the oxide ion concentration in the molten salt by removing the water from the molten salt to bias the equilibrium relationship between the oxide ions and water. That is, the cited reference 1 did not focus on the fact that the water present in the molten salt facilitates the generation of impurities. Moreover, each Example described in Patent Document 1 synthesizes a composite oxide at a relatively low reaction temperature (300 ° C.). Moreover, the raw material of the molten salt is half of which is lithium nitrate.
  • Such a molten salt has a low oxidation state, and thus in Example 3, a spinel-type lithium manganese oxide having a manganese valence of 3.5 is formed, but the manganese valence is tetravalent. Layered rock salt type lithium manganese oxide is not produced. Under the synthesis conditions of such low reaction temperature and low oxidation state, even if the drying step is omitted, it is considered that the mixing of impurities is so small that it can not be detected by a general method such as X-ray diffraction.
  • the present invention can suppress the formation of impurities under reaction conditions capable of synthesizing a lithium-containing composite oxide belonging to a layered rock salt structure, ie, reaction conditions in a relatively high temperature and high oxidation state It aims at providing the manufacturing method of complex oxide.
  • the method for producing a composite oxide of the present invention is a method for producing a lithium-containing composite oxide containing lithium (Li) and one or more metal elements other than lithium and having a crystal structure belonging to a layered rock salt structure, Lithium contained in the lithium-containing composite oxide containing 50 mol% or more of lithium hydroxide in a dehydrated state consisting of lithium hydroxide in a dehydrated state when the total of the metal-containing raw material containing the metal element is 100 mol%
  • the metal-containing raw material is reacted in the molten salt obtained by melting the molten salt raw material containing lithium hydroxide.
  • the molten salt of lithium hydroxide is strongly basic, and in the molten salt of lithium hydroxide, the hydroxide ions decompose into oxygen ions and water, and the water evaporates from the hot molten salt.
  • the molten salt of 350 ° C. or higher containing 50% or more of lithium hydroxide in molar ratio provides a high base concentration and a dehydration environment, and forms a high oxidation state suitable for synthesis of a desired complex oxide.
  • the pH of water in the molten salt becomes very high. Therefore, depending on the type of crucible containing the molten salt, the component of the crucible may elute into the molten salt to form an impurity upon contact with water having a high pH. Furthermore, when the metal-containing raw material is reacted in the presence of water having a high pH, the metal contained in the metal-containing raw material is not sufficiently oxidized, and compounds other than complex oxides having a layered rock salt structure are easily generated as impurities. Become. In addition, when the molten salt material contains water, the water may boil and the molten salt may be scattered when the molten salt material is melted.
  • metal-containing lithium salt is used in the molten salt obtained by melting the molten salt raw material, using dehydrated lithium hydroxide consisting of lithium hydroxide in a dehydrated state as the molten salt raw material. React the ingredients.
  • lithium hydroxide is heated to form a molten salt, if the lithium hydroxide to be melted is in a dehydrated state, high pH water that may be present in the molten salt is reduced, and the above-mentioned impurities are caused. Generation is suppressed. In addition, scattering of molten salt due to boiling of water is also suppressed.
  • dehydrated lithium hydroxide refers to lithium hydroxide in a state essentially free of hydration water, and it does not matter whether dehydration has been carried out in the production process of the production method of the present invention. Absent. That is, even when anhydrous lithium hydroxide is used, it is included in this category, but when commercially available anhydrous lithium hydroxide is used, whether or not the dehydration treatment is carried out in the production process of the anhydrous lithium hydroxide is a problem Absent.
  • the method for producing a composite oxide of the present invention is directed to the synthesis of a lithium-containing composite oxide which contains Li and one or more metal elements other than Li and has a crystal structure belonging to a layered rock salt structure.
  • the lithium-containing composite oxide is a lithium manganese-based oxide, basically the average oxidation number of Mn is four. Even in the complex oxide obtained by the production method of the present invention, there is a possibility that Mn having a valence of less than 4 is present, but by suppressing the formation of impurities, the average oxidation number of Mn is 3.8 or more. It is desirable that the value be as high as 3.9 or more and nearly tetravalent.
  • the average oxidation number of Ni is basically trivalent, but the composite oxidation can be obtained by suppressing the generation of impurities by the production method of the present invention.
  • the average oxidation number of Ni in the whole product is as high as 2.8 or more, and further 2.9 or more, and it is desirable that it be nearly trivalent.
  • Co and Fe which basically have a trivalent value in the lithium-containing composite oxide.
  • LiCoO 2 , LiNioO 2 , LiFeO 2 , Li 2 MnO 3 , LiCo 1/3 Ni 1/3 Mn 1/3 O 2 , LiNi are representative lithium-containing composite oxides whose crystal structure belongs to a layered rock salt structure. 0.5 Mn 0.5 O 2 etc. are mentioned. If these are expressed by a composition formula, xLi 2 M 1 O 3.
  • composition formula Li 1.33-y M 1 0.67-z M 2 y + z O 2 (wherein M 1 is one or more metal elements essentially having tetravalent Mn, M 2 is one or more metal elements,
  • the basic composition is a lithium-containing composite oxide represented by 0 ⁇ y ⁇ 0.33, 0 ⁇ z ⁇ 0.67, and part of Li may be substituted with hydrogen).
  • the composite oxide having the same crystal structure is shown in any of the described methods. It is needless to say that the complex oxide slightly deviated from the above composition formula is also included due to the inevitable loss of Li, M 1 , M 2 or O.
  • the impurities whose formation is suppressed by the method for producing a composite oxide of the present invention there are impurities of insufficient oxidation derived from raw materials, impurities derived from soot, and the like.
  • impurities derived from soot and the like.
  • NiO, LiMnO 2 (orthorhombic layered structure), LiMn 2 O 4 (spinel structure), Mn 2 O 3 , Co 2 O 3 , NiMn 2 O 4 , CoMn 2 O 4 and the like can be mentioned.
  • These impurities present in the lithium-containing composite oxide belonging to the layered rock salt structure can be confirmed by X-ray diffraction (XRD), electron beam diffraction, emission spectral analysis (ICP) or the like.
  • a particulate complex oxide can be obtained. This is because the raw materials are alkali-melted and uniformly mixed in the molten salt. In particular, in the molten salt in which only lithium hydroxide is substantially melted, crystal growth is suppressed even if the reaction temperature is high (for example, 500 ° C. or higher), and a composite oxide in which primary particles are nano-order is obtained.
  • a precursor synthesis step is carried out to make the aqueous solution containing at least two metal elements alkaline to obtain a precipitate, and the precipitate is obtained as at least a part of the metal-containing raw material You may use By using the precipitate as a precursor, a lithium-containing composite oxide can be obtained with high purity.
  • the composite oxide obtained by the method for producing a composite oxide of the present invention can be used as a positive electrode active material of a secondary battery such as a lithium ion secondary battery. That is, the present invention can also be grasped as a positive electrode active material characterized in that the composite oxide obtained by the method for producing a composite oxide of the present invention is included.
  • the method for producing a composite oxide of the present invention it is possible to suppress the generation of impurities which may occur at the time of synthesis of the lithium-containing composite oxide belonging to the layered rock salt structure.
  • results of X-ray diffraction measurement of a lithium-containing composite oxide (Li 2 MnO 3 ) obtained by the method for producing a composite oxide of the present invention and a lithium-containing composite oxide obtained by a method for producing a composite oxide of Comparative Example Indicates Lithium-containing composite oxide (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 ) obtained by the method for producing the composite oxide of the present invention and lithium-containing obtained by the method for producing the composite oxide of the comparative example
  • the result of the X-ray-diffraction measurement of complex oxide is shown.
  • the result of the X-ray-diffraction measurement of various lithium containing complex oxides manufactured by the manufacturing method of complex oxide of this invention is shown.
  • the numerical range “a to b” described in the present specification includes the lower limit a and the upper limit b in that range. Then, the upper limit value and the lower limit value, and the numerical values listed in the examples can be combined arbitrarily to constitute a numerical range.
  • the method for producing a composite oxide according to the present invention is a method for producing a lithium-containing oxide containing Li and one or more metal elements other than Li and having a crystal structure belonging to a layered rock salt structure, mainly a melting reaction step and a recovery step And, if necessary, a raw material preparation step (including a raw material mixture preparation step), a precursor synthesis step and / or a proton substitution step and the like.
  • the raw material preparation step it is desirable to mix the metal-containing raw material and the molten salt raw material.
  • the metal-containing raw material contains the metal element contained in the composite oxide to be synthesized.
  • the molten salt raw material contains lithium hydroxide in a dehydrated state.
  • the metal-containing raw material is a raw material for supplying one or more metal elements other than Li.
  • the metal-containing raw material it is preferable to use one or more metal compounds (first metal compounds) selected from oxides, metal hydroxides and other metal salts containing metal elements.
  • the metal compound is preferably contained as an essential component of the metal-containing raw material.
  • any common metal compound used in the molten salt method can be used. Specifically, if it is a source of Mn, manganese dioxide (MnO 2 ), manganese trioxide (Mn 2 O 3 ), manganese monoxide (MnO), manganese trioxide (Mn 3 O 4 ), and manganese hydroxide (Mn (OH) 2 ), manganese oxyhydroxide (MnOOH), etc. are mentioned.
  • Co source cobalt oxide (CoO, Co 3 O 4) , cobalt nitrate (Co (NO 3) 2 ⁇ 6H 2 O), cobalt hydroxide (Co (OH) 2), cobalt chloride (CoCl 2 ⁇ 6H 2 O), cobalt sulfate (Co (SO 4 ) ⁇ 7H 2 O), and the like.
  • Ni source nickel oxide (NiO), nickel nitrate (Ni (NO 3 ) 2 ⁇ 6H 2 O), nickel sulfate (NiSO 4 ⁇ 6H 2 O), nickel chloride (NiCl 2 ⁇ 6H 2 O), Etc.
  • iron hydroxide Fe (OH) 3
  • iron chloride FeCl 3 ⁇ 6H 2 O
  • iron oxide Fe 2 O 3
  • iron nitrate Fe (NO 3 ) 3 ⁇ 9H 2 O
  • iron sulfate FeSO 4 .9H 2 O
  • a metal compound in which a part of the metal element contained in these oxides, hydroxides or metal salts is substituted with another metal element eg, Cr, Mn, Fe, Co, Ni, Al, Mg, etc.
  • MnO 2 Co source if Mn source Co (OH) 2, if Ni source Ni (OH) 2, if Fe source Fe (OH) 3, is preferably It is easy to obtain, and it is easy to obtain one with relatively high purity.
  • a second metal compound serving as a source of other metal elements may be used.
  • the second metal compound for example, a composite oxide in which tetravalent Mn is substituted by another metal element or a metal element such as a transition metal element can also be manufactured.
  • the second metal compound aluminum hydroxide (Al (OH) 3 ), aluminum nitrate (Al (NO 3 ) 3 9 H 2 O), copper oxide (copper oxide) (in addition to the above-mentioned essential metal-containing raw materials) CuO), copper nitrate (Cu (NO 3) 2 ⁇ 3H 2 O), and the like calcium hydroxide (Ca (OH) 2).
  • Al, Cu and Ca of these metal compounds may be substituted by another metal element. One or more of these may be used as the second metal compound.
  • the metal-containing raw material contains two or more metal elements
  • a metal-containing raw material containing the obtained precipitate can be used.
  • a water-soluble inorganic salt specifically, nitrates, sulfates, chlorides and the like of metal elements are dissolved in water, and alkali metal hydroxide, ammonia water, etc. make the aqueous solution alkaline. Is produced as a precipitate.
  • the lithium-containing composite oxide to be synthesized is a lithium-nickel-based composite oxide containing Ni
  • the production method using a precursor suppresses the formation of byproducts (NiO) that are difficult to remove Because it is
  • the molten salt raw material contains lithium hydroxide.
  • lithium hydroxide either anhydride (LiOH) or hydrate (LiOH ⁇ H 2 O) may be used, but lithium hydroxide to be subjected to the below-mentioned melt reaction step is in a dehydrated state. It needs to be. That is, if it is an anhydride, it can be used as it is, but if it is a hydrate, dehydration is required. If dehydration is necessary, lithium hydroxide needs to be dehydrated at least before the melt reaction step, in other words, before or during the raw material preparation step.
  • the molten salt raw material contains 50 mol% or more of lithium hydroxide based on 100 mol% of the entire molten salt raw material.
  • Lithium hydroxide is used as a raw material for supplying Li.
  • Lithium hydroxide is also used for the purpose of enhancing the oxidizing power of the molten salt because it is the most basic lithium salt. Therefore, in order to efficiently produce a lithium-containing composite oxide having a crystal structure belonging to a layered rock salt structure with high quality, the ratio of lithium hydroxide in the molten salt raw material is preferably 90 mol% or more, more preferably 95 mol % Or more.
  • the molten salt raw material mainly contains lithium hydroxide, but may contain lithium nitrate in the remainder to lower the melting point of the molten salt.
  • Lithium nitrate is a lithium salt with a low melting point, and is used because it is difficult to cause impurities to remain in the produced composite oxide.
  • the molten salt raw material preferably contains lithium nitrate and lithium hydroxide such that the ratio of lithium hydroxide to lithium nitrate (lithium hydroxide / lithium nitrate) is more than 1 and even more than 10 in molar ratio.
  • the ratio of lithium hydroxide to lithium nitrate is more than 1, 1.25 or more, or 1.5 or more, the oxidizing power of the molten salt can be sufficiently increased, and a lithium-containing composite oxide having a layered rock salt structure Is suitable for the synthesis of
  • a molten salt raw material substantially consisting of only lithium hydroxide may be used.
  • the proportion of other components (for example, lithium nitrate) in the molten salt raw material decreases, the melting point of the molten salt rises.
  • the particle diameter of the composite oxide obtained by changing the blend ratio of the molten salt raw material is changed.
  • the particle size of the synthesized particles can be reduced as the oxygen concentration in the melt reaction step described later is increased.
  • the molten salt raw material brings about the desirable high oxidation state for formation of a desired complex oxide by lithium hydroxide being in the above-mentioned content ratio. Therefore, it goes without saying that it is desirable to avoid the use of compounds that affect the oxidation state of the molten salt other than lithium hydroxide and lithium nitrate for the molten salt raw material and the metal-containing raw material.
  • lithium peroxide Li 2 O 2
  • the mixing ratio of the metal-containing raw material and the molten salt raw material may be appropriately selected according to the ratio of Li and metal element contained in the composite oxide to be produced.
  • the ratio of the metal element contained in the metal-containing raw material to the lithium metal contained in the molten salt raw material (the metal element contained in the metal-containing raw material / Li in the molten salt raw material) is 0.01 or more in molar ratio, provided that dare to specify. It is good to make it 2 or less. If it is less than 0.01, the amount of the complex oxide to be formed is smaller than the amount of the molten salt raw material used, which is not desirable in terms of production efficiency.
  • a more desirable ratio (metal element of metal-containing raw material / Li of molten salt raw material) is 0.01 to 0.1, 0.013 to 0.05 and further 0.015 to 0.045 in molar ratio.
  • the blending ratio of the above-described molten salt raw material is defined by the theoretical composition of lithium contained in the target complex oxide (Li of complex oxide / Li of molten salt raw material) with respect to lithium contained in the molten salt raw material Is also possible.
  • the molten salt raw material plays a role not only in the source of lithium but also in adjusting the oxidation state of the molten salt. Therefore, the molten salt raw material contains lithium exceeding the theoretical composition of lithium contained in the composite oxide to be produced.
  • the molar ratio of Li in the complex oxide Li / molten salt raw material may be less than 1, but it is preferably 0.01 to 0.4, and more preferably 0.013 to 0.3, 0.02 to 0.02. 0.2.
  • the amount of the complex oxide to be formed is smaller than the amount of the molten salt raw material used, which is not desirable in terms of production efficiency. Moreover, if it exceeds 0.4, the amount of molten salt for dispersing the metal-containing raw material is insufficient, which may cause aggregation or grain growth of the composite oxide in the molten salt, which is not desirable.
  • lithium hydroxide in a dehydrated state is used. That is, as lithium hydroxide, commercially available anhydrous lithium hydroxide can be used, or it can be used after dehydration of commercially available lithium hydroxide monohydrate.
  • a hydrate you may dry a hydrate independently, but you may dry with a metal-containing raw material after a raw material preparation process. That is, a raw material mixture preparation step of preparing a raw material mixture by mixing the metal-containing raw material and the lithium hydroxide monohydrate-containing molten salt raw material containing at least lithium hydroxide monohydrate before the melting reaction step. And drying the raw material mixture. Drying is preferably carried out using a vacuum dryer, and may be vacuum dried at 80 to 150 ° C.
  • the dried raw material may be subjected to the next melt reaction step as it is. If the molten salt raw material contained in the raw material mixture is an anhydrous lithium hydroxide-containing molten salt raw material containing at least anhydrous lithium hydroxide, the drying step can be omitted.
  • the drying step can be omitted.
  • the melting reaction step is a step of reacting a metal-containing raw material in a molten salt consisting of a molten salt raw material at a reaction temperature of 350 ° C. or more and a melting point or more of the molten salt raw material.
  • the reaction temperature is the temperature of the molten salt in the melting reaction step and may be above the melting point of the molten salt raw material, but if it is less than 350 ° C, the reaction activity of the molten salt is not sufficient and the desired complex oxide having a layered rock salt structure It is difficult to manufacture with high purity.
  • the reaction temperature is 350 ° C. or more, the crystal structure of the obtained composite oxide is stabilized.
  • the reaction temperature is made 350 ° C. or more.
  • the lower limit of the reaction temperature is preferably 400 ° C. or more, 450 ° C. or more, 500 ° C. or more, and further 550 ° C. or more.
  • the higher the reaction temperature the more selectively the complex oxide having a layered rock salt structure can be produced, and the highly crystalline complex oxide can be obtained.
  • lithium nitrate becomes violent at high temperatures (about 600 ° C.). Disassemble.
  • the composite oxide when using a molten salt raw material containing lithium nitrate, the composite oxide can be synthesized under relatively stable conditions if the temperature is 500 ° C. or lower.
  • the molten salt and the metal compound react sufficiently if maintained at this reaction temperature for 30 minutes or more, more preferably for 1 to 6 hours.
  • the melting reaction step is performed in an oxygen-containing atmosphere, for example, in the atmosphere, in an atmosphere containing oxygen gas and / or ozone gas, a lithium-containing composite oxide having a layered rock salt structure is easily obtained in a single phase.
  • the oxygen gas concentration is preferably 20 to 100% by volume, and more preferably 50 to 100% by volume.
  • the particle diameter of the composite oxide to be synthesized tends to be smaller as the oxygen concentration is higher.
  • the proportion of lithium hydroxide contained in the molten salt raw material is high, specifically, when it occupies 90 mol% or more, further 95 mol% or more as defined, the basicity of the molten salt is high and the reaction temperature is also high. Because of the high cost, it is desirable to use a crucible such as gold which does not easily elute components in the molten salt for the reaction.
  • a crucible such as gold which does not easily elute components in the molten salt for the reaction.
  • the method for producing a composite oxide of the present invention even when using a nickel crucible in which Ni is easily eluted in the molten salt, high pH water causing the elution of Ni is almost present in the molten salt Therefore, generation of impurities such as NiO is suppressed.
  • the melting reaction step may include a humidity adjustment step of adjusting the reaction atmosphere to reduce the humidity of the reaction atmosphere.
  • the moisture present in the molten salt can be reduced by using dehydrated lithium hydroxide.
  • water derived from the OH group of lithium hydroxide becomes water vapor and is separated from the molten salt.
  • the humidity of the reaction atmosphere may be adjusted in order to further promote such water desorption. For example, a gas having a humidity lower than that of the reaction atmosphere may be introduced into the reaction atmosphere at the time of raising the temperature of the molten salt raw material in the melting reaction step and / or holding the molten salt at high temperature.
  • a humidity control gas for example, air outside the furnace
  • an oxygen-containing gas such as air or oxygen gas
  • the gas may be dried in advance to reduce the humidity and then introduced into the furnace.
  • the rate of introduction of the humidity control gas is such that the ratio of the introduction amount (unit: L) per minute to the capacity (unit: L) of the furnace is 0.03 to 0.15, and further 0.07 to 0.09. You should do it.
  • the recovery step is a step of recovering the produced composite oxide.
  • the complex oxide produced in the melting reaction step is insoluble in water, so the molten salt is cooled sufficiently to solidify and solidify, and the solid is dissolved in water to form a complex.
  • the oxides are obtained as insolubles.
  • the filtrate obtained by filtering the aqueous solution may be dried to remove the complex oxide.
  • the recovery step may be a step of recovering the composite oxide after gradual cooling after the melting reaction step. That is, the molten salt of high temperature after completion of the reaction may be left in a heating furnace and cooled in the furnace, or may be taken out of the heating furnace and air-cooled at room temperature.
  • a proton substitution step of replacing part of Li of the composite oxide with hydrogen (H) may be performed.
  • part of Li is easily replaced with H by bringing the complex oxide after the recovery step into contact with a solvent such as diluted acid.
  • a composite oxide containing single crystalline primary particles is obtained.
  • the fact that primary particles are substantially single crystal can be confirmed by a high resolution image of a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the complex oxide to be obtained is very fine, and the particle size of the primary particles of the complex oxide is preferably 500 nm or less, further 10 to 200 nm.
  • the particle size can be measured using high resolution TEM images.
  • the primary particle size can also be defined from XRD.
  • the composite oxide may include single crystalline primary particles having a particle diameter of 100 nm or less in the c-axis direction calculated from Scheller's equation.
  • the particle diameter in the c-axis direction of the primary particles of the preferred composite oxide is 5 to 50 nm and further 5.5 to 20 nm.
  • the half-width is the intensity calculated by I max / 2, assuming that the maximum intensity of (001) of Li 2 MnO 3 observed near the diffraction angle (2 ⁇ , CuK ⁇ ray) of 18.5 degrees is I max.
  • the primary particle diameter is too small, the crystal structure tends to collapse due to charge and discharge, which is not preferable because the battery characteristics may deteriorate.
  • the method for producing a complex oxide of the present invention can synthesize lithium-containing complex oxide containing Li and one or more metal elements other than Li and having a crystal structure belonging to a layered rock salt structure, and the generation of impurities is suppressed .
  • the layered rock salt structure is the main component and the generation of impurities is suppressed.
  • the layered structure can be observed with a high resolution image using a high resolution transmission electron microscope (TEM).
  • xLi 2 M 1 O 3 (1-x) LiM 2 O 2 (0 ⁇ x ⁇ 1, and M 1 is essentially a tetravalent Mn.
  • M 2 is at least one metal element containing at least one of trivalent Co, trivalent Ni and trivalent Fe as essential, or two or more metals essentially containing tetravalent Mn Element).
  • 60 atomic percent or less, and 45 atomic percent or less of Li may be substituted with H.
  • M 1 is preferably mostly tetravalent Mn, but less than 50% or even less than 80% may be substituted with another metal element.
  • M 2 is preferably mostly trivalent Co, trivalent Ni or trivalent Fe, but less than 50% or even less than 80% may be substituted by another metal element. Further, if it contains tetravalent Mn to M 2, it is necessary to average valence of M 2 is substituted by other metal elements Ni, Co and the like so as to trivalent. Less than 50%, and preferably less than 80% of M 2 should be substituted with a metal element other than Mn.
  • the substituting element at least one metal element selected from Ni, Al, Co, Fe, Mg, and Ti is preferable from the viewpoint of the chargeable / dischargeable capacity in the case of using the electrode material. It is needless to say that the complex oxide slightly deviated from the above composition formula is also included due to the inevitable loss of Li, M 1 , M 2 or O.
  • the lithium-containing composite oxide obtained by the method for producing a composite oxide according to the present invention has a composition formula: Li 1.33-y M 1 0.67-z M 2 y + z O 2 (M 1 is tetravalent Mn. , And M 2 is at least one metal element containing at least one of trivalent Co, trivalent Ni, and trivalent Fe or at least one metal element having tetravalent Mn.
  • the above metal elements are also represented as 0 ⁇ y ⁇ 0.33 and 0 ⁇ z ⁇ 0.67). The same composition is represented regardless of which notation method is used.
  • the composite oxide obtained by the method for producing a composite oxide of the present invention can be used as a positive electrode active material for a secondary battery such as a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery.
  • a secondary battery such as a non-aqueous electrolyte secondary battery, for example, a lithium ion secondary battery.
  • the non-aqueous electrolyte secondary battery using the positive electrode active material containing the said complex oxide is demonstrated below.
  • a non-aqueous electrolyte secondary battery mainly includes a positive electrode, a negative electrode, and a non-aqueous electrolyte. Further, as in a general non-aqueous electrolyte secondary battery, a separator interposed between the positive electrode and the negative electrode is provided.
  • the positive electrode includes a positive electrode active material capable of inserting and releasing lithium ions, and a binder for binding the positive electrode active material. Furthermore, a conductive aid may be included.
  • the positive electrode active material may contain one or more other positive electrode active materials used in general non-aqueous electrolyte secondary batteries, alone or together with the above-mentioned composite oxide.
  • the binder and the conductive additive are not particularly limited as long as they can be used in general non-aqueous electrolyte secondary batteries.
  • the conductive aid is for securing the electrical conductivity of the electrode, and for example, a mixture of one or more kinds of carbon substance powder such as carbon black, acetylene black and graphite may be used. it can.
  • the binder plays the role of holding the positive electrode active material and the conductive auxiliary material, and, for example, fluorine-containing resin such as polyvinylidene fluoride, polytetrafluoroethylene, fluoro rubber, etc., thermoplastic resin such as polypropylene, polyethylene, etc. It can be used.
  • the negative electrode to be opposed to the positive electrode can be formed by forming a sheet of metal lithium which is a negative electrode active material or by pressing the sheet into a current collector network such as nickel or stainless steel. Instead of lithium metal, lithium alloys or lithium compounds can also be used. Further, as in the case of the positive electrode, a negative electrode comprising a negative electrode active material capable of inserting and extracting lithium ions and a binder may be used.
  • the negative electrode active material it is possible to use, for example, a calcined product of an organic compound such as natural graphite, artificial graphite, or a phenol resin, or a powder of a carbon material such as coke. Similar to the positive electrode, a fluorine-containing resin, a thermoplastic resin or the like can be used as the binder.
  • an active material layer formed by binding at least a positive electrode active material or a negative electrode active material with a binder is generally attached to a current collector. Therefore, the positive electrode and the negative electrode are prepared by preparing a composition for forming an electrode mixture layer including an active material and a binder, and optionally, a conductive auxiliary, and adding an appropriate solvent to form a paste, and then collecting the current collector. After being applied to the surface of the substrate, it can be dried and compressed as necessary to increase the electrode density.
  • metal mesh or metal foil can be used.
  • a porous or non-porous conductive substrate made of a metal material such as stainless steel, titanium, nickel, aluminum, copper or the like or a conductive resin can be mentioned.
  • the porous conductive substrate include a mesh body, a net body, a punching sheet, a lath body, a porous body, a foam, a fiber group molded body such as a non-woven fabric, and the like.
  • non-porous conductive substrates include foils, sheets, films and the like.
  • a conventionally known method such as a doctor blade or a bar coater may be used.
  • NMP N-methyl-2-pyrrolidone
  • MIBK methyl isobutyl ketone
  • an organic solvent-based electrolyte solution in which the electrolyte is dissolved in an organic solvent, a polymer electrolyte in which the electrolyte solution is held in a polymer, or the like can be used.
  • the organic solvent contained in the electrolytic solution or the polymer electrolyte is not particularly limited, but in terms of load characteristics, it is preferable to contain a chain ester.
  • a linear ester for example, linear carbonates represented by dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and organic solvents such as ethyl acetate and methyl propironate can be mentioned.
  • linear esters may be used alone or in combination of two or more, and in particular, for the improvement of low temperature properties, the above linear esters occupy 50% by volume or more in the total organic solvent.
  • the chain ester account for at least 65% by volume in the total organic solvent.
  • esters include, for example, cyclic carbonates represented by ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate, ⁇ -butyrolactone, ethylene glycol sulfite and the like, and ethylene carbonate and propylene are particularly preferred. Esters of cyclic structure such as carbonate are preferred.
  • Such an ester having a high dielectric constant is preferably contained in an amount of 10% by volume or more, particularly 20% by volume or more in the total organic solvent from the viewpoint of discharge capacity. Moreover, from the point of a load characteristic, 40 volume% or less is preferable, and 30 volume% or less is more preferable.
  • LiClO 4 LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiC 4 F 9 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 ( SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiCnF 2n + 1 SO 3 (n ⁇ 2), etc.
  • LiPF 6 and LiC 4 F 9 SO 3 which can provide good charge and discharge characteristics are preferably used.
  • the concentration of the electrolyte in the electrolytic solution is not particularly limited, but is preferably 0.3 to 1.7 mol / dm 3 , particularly about 0.4 to 1.5 mol / dm 3 .
  • the non-aqueous electrolyte may contain an aromatic compound.
  • aromatic compound benzenes having an alkyl group such as cyclohexylbenzene or t-butylbenzene, biphenyl or fluorobenzenes are preferably used.
  • the separator preferably has sufficient strength and can hold a large amount of electrolytic solution, and from such a viewpoint, it is made of polypropylene, polyethylene, a copolymer of propylene and ethylene, etc., and a thickness of 5 to 50 ⁇ m. Microporous films and non-woven fabrics are preferably used. In particular, when a thin separator of 5 to 20 ⁇ m is used, the battery characteristics are easily deteriorated in charge and discharge cycles and high temperature storage, and the safety is also reduced. However, the above composite oxide was used as a positive electrode active material Since the lithium ion secondary battery is excellent in stability and safety, the battery can be stably functioned even using such a thin separator.
  • the shape of the non-aqueous electrolyte secondary battery configured by the above components can be various shapes such as a cylindrical type, a laminated type, and a coin type.
  • a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body.
  • the positive electrode current collector and the negative electrode current collector are connected to the positive electrode terminal and the negative electrode terminal leading to the outside by means of a current collection lead etc.
  • the electrode body is impregnated with the above-mentioned electrolytic solution and sealed in a battery case. An electrolyte secondary battery is completed.
  • the secondary battery using the composite oxide obtained by the manufacturing method of the present invention described above can be suitably used in the field of automobiles as well as in the fields of communication devices such as mobile phones and personal computers, and information related devices.
  • this secondary battery is mounted on a vehicle, the secondary battery can be used as a power source for an electric vehicle.
  • Example 1-1 Synthesis of Li 2 MnO 3
  • a raw material mixture was prepared by mixing 0.20 mol of anhydrous lithium hydroxide (LiOH, 4.79 g) as a molten salt raw material and 0.010 mol of manganese dioxide (MnO 2 , 0.87 g) as a metal-containing raw material.
  • the target product is Li 2 MnO 3
  • the amount of Li of the target product / (the amount of Li of the molten salt raw material)
  • was 0.020 mol / 0.2 mol 0.1.
  • the raw material mixture was poured into a 700 ° C. electric furnace and heated in the 700 ° C. electric furnace for 1 hour. At this time, the raw material mixture in the crucible melted to form a molten salt, and a brown product precipitated. Further, the molten salt did not scatter in the furnace.
  • the crucible containing the molten salt was removed from the electric furnace and cooled at room temperature. After the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water. The water was a black suspension because the product was insoluble in water. The black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed black solid was vacuum dried at 120 ° C. for 12 hours and then crushed using a mortar and pestle.
  • the obtained black powder was subjected to X-ray diffraction (XRD) measurement using a CuK ⁇ ray.
  • XRD X-ray diffraction
  • the measurement results are shown in FIG.
  • the obtained compound was found to be a layered rock salt structure of ⁇ -NaFeO 2 type.
  • the composition obtained from emission spectral analysis (ICP) and average valence analysis of Mn by redox titration was confirmed to be Li 2 MnO 3 . Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as LiMnO 2 were not included.
  • Active oxygen content (%) ⁇ (2 x V2-V1) x 0.00080 / amount of sample ⁇ x 100
  • the units of V1 and V2 are mL, and the unit of sample amount is g.
  • the average valence of Mn was calculated from the amount of Mn (ICP measured value) in the sample and the amount of active oxygen.
  • the obtained black powder was subjected to X-ray diffraction (XRD) measurement using a CuK ⁇ ray.
  • XRD X-ray diffraction
  • Example 1-2 Synthesis of LiCo 1/3 Ni 1/3 Mn 1/3 O 2
  • the mixed phase of LiCo 1/3 Ni 1/3 Mn 1/3 O 2 was synthesized by the following procedure.
  • a precursor (1.0 g) was added as a metal-containing raw material to 0.30 mol of anhydrous lithium hydroxide (LiOH, 7.2 g) as a molten salt raw material to prepare a raw material mixture.
  • anhydrous lithium hydroxide LiOH, 7.2 g
  • the raw material mixture was poured, transferred to an electric furnace set at 700 ° C., and heated at 700 ° C. in an oxygen atmosphere for 2 hours. At this time, the raw material mixture was melted to form a molten salt, and a dark brown product precipitated. Further, the molten salt did not scatter in the furnace.
  • the crucible containing the molten salt was removed from the electric furnace and cooled at room temperature. After the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water. The water was a black suspension because the product was insoluble in water. The black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper.
  • the resulting filtrate was filtered with thorough washing with acetone.
  • the washed black solid was vacuum dried at 120 ° C. for 6 hours, and then ground using a mortar and pestle.
  • the obtained black powder was subjected to X-ray diffraction (XRD) measurement using a CuK ⁇ ray.
  • XRD X-ray diffraction
  • the measurement results are shown in FIG.
  • the obtained compound was found to be a layered rock salt structure of ⁇ -NaFeO 2 type.
  • the composition obtained from emission spectral analysis (ICP) and average valence analysis of Mn by redox titration was confirmed to be LiCo 1/3 Ni 1/3 Mn 1/3 O 2 . Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as NiO were not included.
  • the obtained black powder was subjected to X-ray diffraction (XRD) measurement using a CuK ⁇ ray.
  • XRD X-ray diffraction
  • Example 2-1 Synthesis of Li 2 MnO 3
  • Li 2 MnO 3 A molten salt raw material was prepared by mixing 0.15 mol of lithium hydroxide monohydrate (LiOH.H 2 O, 6.3 g) and 0.10 mol of lithium nitrate (LiNO 3 , 6.9 g).
  • 0.010 mol of manganese dioxide (MnO 2 , 0.87 g) was added as a metal-containing raw material to prepare a raw material mixture.
  • the raw material mixture was put in a mullite crucible and vacuum dried at 120 ° C. for 12 hours in a vacuum dryer.
  • the drier was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, immediately transferred to an electric furnace heated to 350 ° C., and heated at 350 ° C. for 2 hours in an oxygen atmosphere (100% oxygen gas concentration). At this time, the raw material mixture was melted to form a molten salt, and a black product was precipitated. Further, the molten salt did not scatter in the furnace.
  • the crucible containing the molten salt was removed from the electric furnace and cooled at room temperature. After the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water. The water became a black suspension because the black product was insoluble in water. The black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper. The resulting filtrate was filtered while being thoroughly washed with ion exchange water. The washed black solid was vacuum dried at 120 ° C. for 6 hours, and then ground using a mortar and pestle.
  • the obtained black powder was subjected to X-ray diffraction (XRD) measurement using a CuK ⁇ ray.
  • XRD X-ray diffraction
  • the measurement results are shown in FIG.
  • the obtained compound was found to be a layered rock salt structure of ⁇ -NaFeO 2 type.
  • the composition obtained from emission spectral analysis (ICP) and average valence analysis of Mn by redox titration was confirmed to be Li 2 MnO 3 . Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as LiMnO 2 were not included.
  • Example 2-2 Synthesis of Li 2 MnO 3
  • the molar ratio of lithium hydroxide monohydrate (LiOH ⁇ H 2 O) to lithium nitrate (LiNO 3 ) is 5: 1, and the temperature and time of the molten salt reaction step are 3 hours at 500 ° C. in air.
  • lithium manganate was synthesized. Specifically, 0.5 mol of lithium hydroxide monohydrate (LiOH.H 2 O, 21.0 g) and 0.10 mol of lithium nitrate (LiNO 3 , 6.9 g) are mixed, .10 mol of manganese dioxide (MnO 2 , 0.87 g) was added to prepare a raw material mixture.
  • the XRD measurement was performed about the obtained black powder.
  • the measurement results are shown in FIG. According to XRD, ICP and average valence analysis of Mn, the obtained lithium manganate was found to be Li 2 MnO 3 having a layered rock salt structure of ⁇ -NaFeO 2 type. Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as LiMnO 2 were not included.
  • Example 2-3 Synthesis of 0.5 (Li 2 MnO 3 ) .0.5 (LiCoO 2 )>
  • the mixed phase of Li 2 MnO 3 and LiCoO 2 was synthesized by the following procedure.
  • a molten salt raw material was prepared by mixing 0.20 mol of lithium hydroxide monohydrate (LiOH ⁇ H 2 O, 8.4 g) and 0.10 mol of lithium nitrate (LiNO 3 , 6.9 g).
  • a precursor 1.0 g was added thereto as a metal-containing raw material to prepare a raw material mixture. Below, the synthetic
  • the transition metal element content of this precursor 1g is 0.0128 mol.
  • the raw material mixture was put in a mullite crucible and vacuum dried at 120 ° C. for 24 hours in a vacuum drier.
  • the drier was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, immediately transferred to an electric furnace heated to 350 ° C., and heated at 350 ° C. in an oxygen atmosphere for 2 hours. At this time, the raw material mixture was melted to form a molten salt, and a black product was precipitated. Further, the molten salt did not scatter in the furnace.
  • the crucible containing the molten salt was removed from the electric furnace and cooled at room temperature. After the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water. The water became a black suspension because the black product was insoluble in water. The black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper. The resulting filtrate was filtered while being thoroughly washed with ion exchange water. The washed black solid was vacuum dried at 120 ° C. for 6 hours, and then ground using a mortar and pestle.
  • the XRD measurement using CuK alpha ray was performed about the obtained black powder.
  • the measurement results are shown in FIG.
  • the obtained compound was found to be a layered rock salt structure of ⁇ -NaFeO 2 type.
  • the composition was confirmed to be 0.5Li 2 MnO 3 .0.5LiCoO 2 . Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as LiMnO 2 were not included.
  • a molten salt raw material was prepared by mixing 0.30 mol of lithium hydroxide monohydrate (LiOH.H 2 O, 12.6 g) and 0.10 mol of lithium nitrate (LiNO 3 , 6.9 g).
  • a precursor 1.0 g was added thereto as a metal-containing raw material to prepare a raw material mixture. Below, the synthetic
  • the obtained precursor was confirmed by X-ray diffraction measurement to be a mixed phase of Mn 3 O 4 , Co 3 O 4 and NiO. Therefore, the transition metal element content of this precursor 1g is 0.013 mol.
  • the raw material mixture was put in a mullite crucible and vacuum dried at 120 ° C. for 12 hours in a vacuum drier.
  • the drier was returned to atmospheric pressure, the crucible containing the raw material mixture was taken out, immediately transferred to an electric furnace heated to 450 ° C., and heated at 450 ° C. for 4 hours in an oxygen atmosphere. At this time, the raw material mixture was melted to form a molten salt, and a black product was precipitated. Further, the molten salt did not scatter in the furnace.
  • the crucible containing the molten salt was removed from the electric furnace and cooled at room temperature. After the molten salt was sufficiently cooled and solidified, it was immersed in 200 mL of ion-exchanged water with stirring, whereby the solidified molten salt was dissolved in water. The water became a black suspension because the black product was insoluble in water. The black suspension was filtered to give a clear filtrate and a filter cake of black solid on filter paper. The resulting filtrate was filtered while being thoroughly washed with ion exchange water. The washed black solid was vacuum dried at 120 ° C. for 6 hours, and then ground using a mortar and pestle. The XRD measurement using CuK alpha ray was performed about the obtained black powder.
  • the obtained compound was found to be a layered rock salt structure of ⁇ -NaFeO 2 type.
  • the composition was confirmed to be 0.5 (Li 2 MnO 3 ) .0.5 (LiCo 1/3 Ni 1/3 Mn 1/3 O 2 ). The Since no peak indicating the presence of impurities was detected in the XRD measurement results, the impurities such as LiMnO 2 were not included.
  • Examples 1-1 and 1-2 anhydrous lithium hydroxide was used as the molten salt raw material.
  • Examples 2-1 to 2-4 lithium hydroxide monohydrate was used as the molten salt raw material, but it was dried and then heated to form a molten salt. That is, in these examples, the reaction was performed in a molten salt in which lithium hydroxide in a dehydrated state was heated to form a molten salt.
  • the reaction was performed in a molten salt in which lithium hydroxide in a dehydrated state was heated to form a molten salt.
  • any of the composite oxides synthesized in Examples 1-1 and 1-2 and Comparative Examples 1-1 and 1-2 can be used as a positive electrode active material of a non-aqueous electrolyte secondary battery.
  • the complex oxides synthesized in Comparative Examples 1-1 and 1-2 are, as the positive electrode active material, due to the presence of impurities. It is speculated that the battery performance will decrease when used.

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Abstract

L'invention concerne un procédé pour la production d'un oxyde composite contenant du lithium, par lequel il devient possible de synthétiser un oxyde composite contenant du lithium qui contient du Li et au moins un élément métallique autre que le Li et a une structure cristalline appartenant à une structure stratifiée de sel gemme, et il devient aussi possible de prévenir la formation d'impuretés sous des conditions de réaction à haute température/hautement oxydatives. Le procédé comprend: une étape de réaction en fusion consistant à mettre en réaction un matériau brut contenant un métal qui contient un élément métallique dans un sel fondu, qui est préparé en faisant fondre un matériau brut de sel fondu, à une température de réaction qui est supérieure ou égale à 350˚C et est supérieure ou égale à la température de fusion du matériau brut de sel fondu, dans lequel le matériau brut de sel fondu contient de l'hydroxyde de lithium déshydraté, qui comprend de l'hydroxyde de lithium déshydraté, dans une quantité de 50% en mole ou plus par rapport à la quantité totale, c'est-à-dire, 100% en mole, du matériau brut de sel fondu, et contient aussi du Li à un rapport molaire plus grand que la teneur théorique en Li dans l'oxyde composite contenant du lithium; et une étape de récolte consistant à collecter de l'oxyde composite contenant du lithium produit dans l'étape de réaction de fusion.
PCT/JP2012/001528 2011-03-22 2012-03-06 Procédé pour la production d'oxyde composite contenant du lithium, matériau actif d'électrode positive et batterie secondaire WO2012127796A1 (fr)

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KR20220025422A (ko) * 2020-08-24 2022-03-03 (주)한국워터테크놀로지 전기 삼투 방식을 이용한 양극 활물질 탈수 장치 및 그 탈수 장치를 포함하는 탈수 설비

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JP2013175302A (ja) * 2012-02-23 2013-09-05 Toyota Industries Corp 複合酸化物の製造方法、二次電池用正極活物質および二次電池
WO2014128904A1 (fr) * 2013-02-22 2014-08-28 株式会社 日立製作所 Circuit de commande de batterie, système de batterie, et corps mobile et système de stockage d'énergie les comprenant
WO2014184861A1 (fr) * 2013-05-14 2014-11-20 株式会社日立製作所 Système de batterie, corps mobile et système de stockage d'énergie doté d'un système de batterie, et procédé de commande du système de batterie
KR20220025422A (ko) * 2020-08-24 2022-03-03 (주)한국워터테크놀로지 전기 삼투 방식을 이용한 양극 활물질 탈수 장치 및 그 탈수 장치를 포함하는 탈수 설비
WO2022045525A1 (fr) * 2020-08-24 2022-03-03 (주)한국워터테크놀로지 Appareil de déshydratation de matériau actif de cathode au moyen de l'électro-osmose, et équipement de déshydratation comprenant un appareil de déshydratation
KR102423486B1 (ko) 2020-08-24 2022-07-21 (주)한국워터테크놀로지 전기 삼투 방식을 이용한 양극 활물질 탈수 장치 및 그 탈수 장치를 포함하는 탈수 설비

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