+

WO2018181465A1 - Procédé de production d'oxyde métallique composite de lithium - Google Patents

Procédé de production d'oxyde métallique composite de lithium Download PDF

Info

Publication number
WO2018181465A1
WO2018181465A1 PCT/JP2018/012725 JP2018012725W WO2018181465A1 WO 2018181465 A1 WO2018181465 A1 WO 2018181465A1 JP 2018012725 W JP2018012725 W JP 2018012725W WO 2018181465 A1 WO2018181465 A1 WO 2018181465A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
cleaning liquid
metal oxide
composite metal
lithium composite
Prior art date
Application number
PCT/JP2018/012725
Other languages
English (en)
Japanese (ja)
Inventor
佐藤　雄一
公保 中尾
裕介 前田
Original Assignee
住友化学株式会社
株式会社田中化学研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社, 株式会社田中化学研究所 filed Critical 住友化学株式会社
Priority to KR1020197024218A priority Critical patent/KR102545342B1/ko
Priority to CN201880014933.2A priority patent/CN110366541B/zh
Publication of WO2018181465A1 publication Critical patent/WO2018181465A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • 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
    • 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 composite metal oxide.
  • the lithium composite metal oxide is used as a positive electrode active material for a lithium secondary battery.
  • Lithium secondary batteries have already been put into practical use not only for small power sources for mobile phones and notebook computers, but also for medium and large power sources for automobiles and power storage.
  • the method for producing a lithium composite metal oxide generally includes a raw material mixing step, a firing step, and a cleaning step.
  • Water is used as the cleaning liquid used in the cleaning process.
  • Patent Document 1 discloses a process in which a lithium composite metal oxide having a specific composition is baked and then washed with water stirring at a ratio of 50 to 200 parts by weight of water with respect to 100 parts by weight of the lithium composite metal oxide. The manufacturing method of the positive electrode active material for non-aqueous electrolyte secondary batteries which has this is described.
  • lithium secondary batteries are required to have further improved battery characteristics such as high initial charge / discharge efficiency, and positive electrode active materials suitable for them.
  • This invention is made
  • the present invention includes the following [1] to [5].
  • a second cleaning step for cleaning with a second cleaning liquid wherein the first cleaning liquid is an alkaline cleaning liquid containing a compound containing an alkali metal, and the second cleaning liquid contains an alkali metal.
  • An alkaline cleaning liquid comprising at least one of a compound and an alkaline compound not containing an alkali metal, wherein an alkali metal concentration relative to a total mass of the first cleaning liquid in the first cleaning liquid is the second cleaning liquid.
  • M is one or more metal elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V, and 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, and 0 ⁇ w ⁇ 0.1.]
  • y + z + w ⁇ 0.3 The method for producing a lithium composite metal oxide according to [2].
  • a method for producing a lithium composite metal oxide suitable for a lithium secondary battery having high initial charge / discharge efficiency can be provided.
  • the production process of the metal composite compound and the production process of the lithium composite metal oxide are optional steps, and the subsequent first cleaning step and second cleaning step are essential. Prepare as a process. Hereinafter, each step will be described.
  • a metal other than lithium that is, an essential metal composed of Ni, Co, and Mn is included, and optionally Fe, Cu, Ti, Mg, Al, Preparing a metal composite compound containing any one or more of W, B, Mo, Nb, Zn, Sn, Zr, Ga and V, and firing the metal composite compound with an appropriate lithium salt.
  • a metal complex compound a metal complex hydroxide or a metal complex oxide is preferable.
  • the metal complex compound can be produced by a generally known batch coprecipitation method or continuous coprecipitation method.
  • the manufacturing method will be described in detail by taking a metal composite hydroxide containing nickel, cobalt, and manganese as an example.
  • the metal complex hydroxide is co-precipitation, in particular by a continuous method described in 2002-201028 JP-nickel salt solution, cobalt salt solution, is reacted manganese salt solution and a complexing agent, Ni ( 1-yz) produced by precipitating a composite metal hydroxide represented by Co y Mn z (OH) 2 (where 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4) be able to.
  • nickel salt which is the solute of the said nickel salt solution For example, any one of nickel sulfate, nickel nitrate, nickel chloride, and nickel acetate can be used.
  • cobalt salt that is a solute of the cobalt salt solution for example, any one of cobalt sulfate, cobalt nitrate, and cobalt chloride can be used.
  • manganese salt that is a solute of the manganese salt solution for example, any one of manganese sulfate, manganese nitrate, and manganese chloride can be used.
  • the above metal salt is used in a proportion corresponding to the composition ratio of Ni (1-yz) Co y Mn z (OH) 2 . That is, each of the molar ratios of nickel, cobalt, and manganese in the mixed solution containing the metal salt corresponds to (1-yz): y: z in the composition formula (I) of the lithium composite metal compound. Define the amount of metal salt. Moreover, water is used as a solvent.
  • the complexing agent is capable of forming a complex with nickel, cobalt, and manganese ions in an aqueous solution.
  • an ammonium ion supplier ammonium sulfate, ammonium chloride, ammonium carbonate, ammonium fluoride, etc.
  • hydrazine examples include ethylenediaminetetraacetic acid, nitrilotriacetic acid, uracil diacetic acid, and glycine.
  • the complexing agent may not be included if desired.
  • the amount of the complexing agent contained in the mixed solution containing the nickel salt solution, the cobalt salt solution, the manganese salt solution and the complexing agent is greater than 0 and 2.0 or less.
  • an alkali metal hydroxide for example, sodium hydroxide or potassium hydroxide
  • an alkali metal hydroxide for example, sodium hydroxide or potassium hydroxide
  • the temperature of the reaction vessel is controlled within a range of, for example, 20 ° C. or more and 80 ° C. or less, preferably 30 ° C. or more and 70 ° C. or less.
  • it is preferably controlled within a range of pH 11 or more and pH 13 or less, and the substance in the reaction vessel is appropriately stirred.
  • the reaction vessel is of a type that causes the formed reaction precipitate to overflow for separation.
  • the finally obtained lithium composite metal oxide is controlled to have desired physical properties. Can do.
  • the obtained reaction precipitate is washed with water and then dried to isolate the nickel cobalt manganese metal composite hydroxide as the nickel cobalt manganese metal composite compound. Moreover, you may wash
  • nickel cobalt manganese metal composite hydroxide is manufactured, but nickel cobalt manganese metal composite oxide may be prepared.
  • a metal composite hydroxide containing nickel, cobalt, manganese and tungsten may be prepared.
  • a metal composite hydroxide containing nickel, cobalt and manganese other than tungsten is prepared by the above method, and then the aqueous solution containing tungsten oxide is dried and deposited on the metal composite hydroxide containing nickel, cobalt and manganese.
  • a metal composite hydroxide containing nickel, cobalt, manganese and tungsten can be prepared.
  • the dried metal composite hydroxide containing nickel, cobalt and manganese is 100 ° C. to 200 ° C.
  • a method of spraying an aqueous solution containing tungsten oxide while heating at a temperature may be used.
  • the concentration of tungsten oxide contained in the aqueous solution containing tungsten oxide is, for example, 1% by mass or more and 10% by mass or less.
  • the aqueous solution containing tungsten oxide may contain a lithium salt such as lithium hydroxide.
  • the concentration of lithium hydroxide contained in the aqueous solution containing tungsten oxide is 1% by mass or more and 10% by mass or less.
  • the metal composite hydroxide containing nickel, cobalt, manganese, and tungsten may contain a metal element other than tungsten as the optional metal.
  • the metal composite oxide or hydroxide is dried and then mixed with a lithium salt.
  • the drying conditions are not particularly limited, but, for example, conditions in which the metal composite oxide or hydroxide is not oxidized and reduced (that is, the oxide is maintained as an oxide, the hydroxide is maintained as a hydroxide).
  • Conditions conditions under which the metal composite hydroxide is oxidized (ie, conditions under which the hydroxide is oxidized into oxide), conditions under which the metal composite oxide is reduced (ie under conditions under which the oxide is reduced into hydroxide) Any of the above conditions may be used.
  • An inert gas such as nitrogen, helium and argon may be used for conditions where oxidation and reduction are not performed.
  • any one of lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium hydroxide, lithium hydroxide hydrate, lithium oxide and lithium fluoride, or a mixture of two or more can be used. In these, any one or both of lithium hydroxide and lithium carbonate are preferable.
  • Classification may be appropriately performed after the metal composite oxide or hydroxide is dried. The above lithium salt and metal composite metal hydroxide are used in consideration of the composition ratio of the final object.
  • the lithium salt and the composite metal hydroxide are Li x Ni (1-yz) Co y Mn z O 2 (where 0 ⁇ x ⁇ 0. 2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4).
  • a lithium-nickel cobalt manganese composite oxide is obtained by firing a mixture of a nickel cobalt manganese metal composite hydroxide and a lithium salt. For the firing, dry air, an oxygen atmosphere, an inert atmosphere, or the like is used according to a desired composition, and a plurality of heating steps are performed if necessary.
  • the firing temperature of the metal composite oxide or hydroxide and lithium salt such as lithium hydroxide and lithium carbonate is not particularly limited, but is preferably 600 ° C. or higher and 1100 ° C. or lower, and preferably 750 ° C. or higher and 1050 ° C. More preferably, it is 800 ° C. or lower and more preferably 800 ° C. or higher and 1025 ° C. or lower.
  • the firing time is preferably 3 hours or more and 50 hours or less. When the firing time exceeds 50 hours, the battery performance tends to be substantially inferior due to volatilization of lithium. That is, if the firing time is within 50 hours, the volatilization of lithium can be suppressed. If the firing time is less than 3 hours, the crystal growth is poor and the battery performance tends to be poor. When the firing time is 3 hours or more, the crystal development is good and the battery performance tends to be good.
  • the firing time is preferably 1 hour or more and 30 hours or less for the total time from the start of raising the temperature to the end of temperature holding. When the total time is 30 hours or less, the volatilization of Li can be prevented and the battery performance can be prevented from deteriorating.
  • the time from the start of the temperature rise to the firing temperature is preferably 0.5 hours or more and 20 hours or less. When the time from the start of temperature rise to the firing temperature is within this range, a more uniform lithium composite metal oxide can be obtained.
  • the temperature for such preliminary firing is preferably in the range of 300 ° C. to 850 ° C. for 1 hour to 10 hours.
  • the present embodiment includes a first cleaning process and a second cleaning process for cleaning the cleaning product obtained in the first cleaning process.
  • the first cleaning step is a step of cleaning and removing the remaining lithium carbonate derived from the raw material.
  • the first cleaning step is a step of cleaning the lithium composite metal compound and removing residual lithium carbonate derived from the raw material.
  • the second cleaning step is a step of cleaning and removing residual components of the cleaning liquid used in the first cleaning step.
  • the second cleaning step is a step of cleaning the lithium composite metal compound and removing the cleaning liquid used in the first cleaning step remaining in the lithium composite metal oxide.
  • removing does not mean only when the object is completely removed, but is interpreted to include the case where the object remains partially.
  • the amount of lithium carbonate contained in the lithium composite metal oxide after the first cleaning step should be less than the amount of lithium carbonate contained in the lithium composite metal oxide before the first cleaning step, Lithium carbonate may remain in the lithium composite metal oxide.
  • the first cleaning liquid is an alkaline cleaning liquid containing a compound containing an alkali metal.
  • the compound containing an alkali metal contained in the alkaline cleaning liquid include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (lithium carbonate), Na 2 CO 3.
  • examples thereof include one or more anhydrides selected from the group consisting of (sodium carbonate) and K 2 CO 3 (potassium carbonate), and hydrates thereof. From the viewpoint of further suppressing elution of lithium from the lithium composite metal oxide, lithium hydroxide or lithium carbonate is preferable, and lithium hydroxide is more preferable.
  • the first cleaning liquid can be prepared by dissolving the alkali metal-containing compound in water.
  • concentration of the compound containing an alkali metal is preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more with respect to the total mass of the first cleaning liquid. Moreover, 30 mass% or less is preferable, 25 mass% or less is more preferable, and 20 mass% or less is especially preferable.
  • the upper limit and the lower limit of the concentration of the compound containing an alkali metal can be arbitrarily combined.
  • the concentration of the compound containing an alkali metal is preferably 1% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and more preferably 10% by mass to 20% by mass with respect to the total mass of the first cleaning liquid. A mass% or less is particularly preferred.
  • cleaning liquid is more than the said lower limit, the elution of lithium from a lithium composite metal oxide can be suppressed more. It can suppress that the compound containing an alkali metal remains in the lithium complex metal oxide manufactured because the density
  • the alkali metal concentration relative to the total mass of the first cleaning liquid in the first cleaning liquid is greater than the alkali metal concentration relative to the total mass of the second cleaning liquid in the second cleaning liquid described later. It is also characterized by high.
  • the concentration of the compound containing an alkali metal with respect to the total mass of the first cleaning liquid in the first cleaning liquid is a compound containing the alkali metal with respect to the total mass of the second cleaning liquid in the second cleaning liquid. Higher than the concentration of.
  • the ratio of the lithium composite metal oxide after firing to the total mass of the first cleaning liquid in the first cleaning step is preferably 30 to 100% by mass, and more preferably 40 to 60% by mass.
  • the ratio of the lithium composite metal oxide after firing to the total mass of the first cleaning liquid is 30 to 100% by mass, elution of lithium from the lithium composite metal oxide can be further suppressed, and the manufactured lithium composite metal It can suppress that the compound containing an alkali metal remains in an oxide.
  • the elution of the lithium component in the lithium composite metal oxide can be suppressed in the cleaning liquid by performing the cleaning process using the first cleaning liquid. For this reason, the concentration gradient of the lithium component on the particle surface of the lithium composite metal oxide to be produced is small, and the remaining lithium carbonate derived from the raw material can be removed while maintaining the lithium component concentration on the particle surface high. Conceivable. In other words, while maintaining a state where the concentration gradient of the lithium component from the inside of the lithium composite metal oxide toward the particle surface is small and the decrease in the lithium component concentration on the particle surface is suppressed, Can be removed. Thereby, the lithium composite metal oxide suitable for a lithium secondary battery with high initial charge / discharge efficiency can be manufactured.
  • the second cleaning step includes a second step of cleaning the lithium composite metal oxide with the second cleaning liquid.
  • the second cleaning liquid is an alkaline cleaning liquid.
  • the second cleaning liquid is an alkaline cleaning liquid containing at least one of a compound containing an alkali metal as an alkali component and an alkaline compound not containing an alkali metal.
  • Examples of the compound containing an alkali metal contained in the second cleaning liquid include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (lithium carbonate), Na 2.
  • the second cleaning liquid is preferably a lithium hydroxide aqueous solution. As described above, ammonia water can also be used as the second cleaning liquid.
  • the alkaline cleaning liquid as the second cleaning liquid may be a cleaning liquid containing an alkali metal as an alkali component, or may use at least one of ammonia water and ammonium carbonate water as a cleaning liquid without containing an alkali metal as an alkali component.
  • a cleaning liquid containing an alkali metal as an alkali component and further containing at least one of ammonia water and ammonium carbonate water may be used.
  • the second alkali cleaning liquid contains an alkali metal as an alkali component
  • the alkali metal concentration in the first cleaning liquid is higher than the alkali metal concentration in the second cleaning liquid.
  • the ammonia and ammonium ion concentrations in the second alkaline cleaning liquid are as follows. It may be higher than the concentration of alkali metal in the cleaning liquid.
  • the concentration of the alkali metal with respect to the total mass of the first cleaning liquid in the first cleaning liquid is preferably twice or more as compared with the concentration of the alkali metal with respect to the total mass of the second cleaning liquid in the second cleaning liquid. .
  • the second cleaning liquid can be prepared by dissolving the alkali component in water.
  • the concentration of the alkali component in the second cleaning liquid with respect to the total mass of the second cleaning liquid is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and particularly preferably 2.0% by mass or more.
  • the upper limit of the concentration of the aqueous solution of the alkali component only needs to be lower than the concentration of the alkaline component in the first cleaning liquid, and is preferably 30% by mass or less, for example, 20% by mass with respect to the total mass of the second cleaning liquid. % Or less is more preferable, and 10% by mass or less is particularly preferable.
  • the upper limit value and the lower limit value of the concentration of the alkali component in the second cleaning liquid can be arbitrarily combined.
  • the concentration of the alkali component in the second cleaning liquid is preferably 0.1% by mass or more and 30% by mass or less, more preferably 1.0% by mass or more and 20% by mass or less, with respect to the total mass of the second cleaning liquid. 2.0 mass% or more and 10 mass% or less are especially preferable.
  • the concentration of the alkali component in the second cleaning liquid is the alkali metal relative to the total mass of the second cleaning liquid.
  • the ratio of the lithium composite metal oxide after firing to the total mass of the second cleaning liquid in the second cleaning step is preferably 3 to 30% by mass, and more preferably 5 to 20% by mass.
  • the ratio of the lithium composite metal oxide after firing to the total mass of the second cleaning liquid in the second cleaning step is 3 to 30% by mass, the lithium component contained in the manufactured lithium composite metal oxide is eluted.
  • the residual component of the first cleaning liquid can be removed by cleaning while suppressing this.
  • the residual component of the first cleaning liquid can be removed by cleaning while suppressing the remaining alkali metal-containing compound contained in the second cleaning liquid.
  • the lithium composite metal oxide is put into an aqueous solution of each cleaning liquid and stirred.
  • the method a method in which an aqueous solution of each cleaning solution is used as shower water, and the lithium composite metal oxide is washed with the first cleaning solution, and then the wet cake of the lithium composite metal oxide separated from the first cleaning solution
  • the method (reslurry or repulp) which is put into the washing liquid and stirred.
  • the lithium composite metal oxide is added to the first cleaning liquid and stirred, the lithium composite metal oxide is separated from the first cleaning liquid, and then the second cleaning liquid is used as shower water. Examples include a method of applying to the lithium composite metal oxide after separation.
  • the lithium composite metal oxide is separated from the washing solution by filtration or the like. Thereafter, it is dried, pulverized as necessary, classified as appropriate, and used as a positive electrode active material applicable to a lithium secondary battery.
  • a step of depositing Al 2 O 3 on the surface of the obtained lithium composite metal oxide and baking it may be performed.
  • firing conditions an oxygen atmosphere is preferable.
  • the firing temperature is preferably 300 to 850 ° C, more preferably 400 to 780 ° C.
  • the firing time is preferably 1 to 30 hours, and more preferably 3 to 10 hours.
  • the produced lithium composite metal oxide is preferably represented by the following composition formula (I).
  • M is one or more metal elements selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga and V, and 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.4, 0 ⁇ z ⁇ 0.4, and 0 ⁇ w ⁇ 0.1 are satisfied.
  • x in the composition formula (I) is preferably more than 0, more preferably 0.01 or more, and particularly preferably 0.02 or more. . Further, from the viewpoint of obtaining a lithium secondary battery having higher initial Coulomb efficiency, x in the composition formula (I) is preferably 0.1 or less, more preferably 0.08 or less, and 0.06. It is particularly preferred that The upper limit value and the lower limit value of x can be arbitrarily combined. For example, x exceeds 0 and is preferably 0.1 or less, more preferably 0.01 or more and 0.08 or less, and particularly preferably 0.02 or more and 0.06 or less.
  • y in the composition formula (I) is preferably 0.005 or more, more preferably 0.01 or more, and 0.05 or more. It is particularly preferred. Further, from the viewpoint of obtaining a lithium secondary battery having high thermal stability, y in the composition formula (I) is more preferably 0.35 or less, and particularly preferably 0.33 or less.
  • the upper limit value and the lower limit value of y can be arbitrarily combined. For example, y is preferably 0.005 or more and 0.35 or less, more preferably 0.01 or more and 0.33 or less, and particularly preferably 0.05 or more and 0.33 or less.
  • z in the composition formula (I) is preferably 0.01 or more, more preferably 0.03 or more, and 0.1 or more. It is particularly preferred. Further, from the viewpoint of obtaining a lithium secondary battery having high storage characteristics at a high temperature (for example, in an environment of 60 ° C.), z in the composition formula (I) is preferably 0.4 or less, and is 0.38 or less. Is more preferable, and it is especially preferable that it is 0.35 or less.
  • the upper limit value and lower limit value of z can be arbitrarily combined. For example, z is preferably 0.01 or more and 0.4 or less, more preferably 0.03 or more and 0.38 or less, and particularly preferably 0.1 or more and 0.35 or less.
  • w in the composition formula (I) is preferably more than 0, more preferably 0.0005 or more, and 0.001 or more. Particularly preferred. Further, from the viewpoint of obtaining a lithium secondary battery having a high discharge capacity at a high current rate, w in the composition formula (I) is preferably 0.09 or less, more preferably 0.08 or less, and 0 0.07 or less is particularly preferable.
  • the upper limit value and the lower limit value of w can be arbitrarily combined. For example, w exceeds 0 and is preferably 0.09 or less, more preferably 0.0005 or more and 0.08 or less, and particularly preferably 0.001 or more and 0.07 or less.
  • M in the composition formula (I) is one or more metals selected from the group consisting of Fe, Cu, Ti, Mg, Al, W, B, Mo, Nb, Zn, Sn, Zr, Ga, and V. To express.
  • M in the composition formula (I) is one or more metals selected from the group consisting of Ti, Mg, Al, W, B, and Zr. From the viewpoint of obtaining a lithium secondary battery with high thermal stability, it is more preferably one or more metals selected from the group consisting of Al, W, B, and Zr.
  • the crystal structure of the lithium nickel composite oxide is a layered structure, and more preferably a hexagonal crystal structure or a monoclinic crystal structure.
  • the hexagonal crystal structures are P3, P3 1 , P3 2 , R3, P-3, R-3, P312, P321, P3 1 12, P3 1 21, P3 2 12, P3 2 21, R32, P3m1, P31m, P3c1, P31c, R3m, R3c, P-31m, P-31c, P-3m1, P-3c1, R-3m, R-3c, P6, P6 1 , P6 5 , P6 2 , P6 4 , P6 3 , P-6, P6 / m, P6 3 / m, P622, P6 1 22, P6 5 22, P6 2 22, P6 4 22, P6 3 22, P6 mm, P6 cc, P6 3 cm, P6 3 mc, P- It belongs to any one space group selected from the group consisting of 6m2, P-6c2, P-62m, P-62c, P6 / mmm, P6 / mcc, P6 3 / mcm, P-
  • Monoclinic crystal structures are P2, P2 1 , C2, Pm, Pc, Cm, Cc, P2 / m, P2 1 / m, C2 / m, P2 / c, P2 1 / c, and C2. It belongs to any one space group selected from the group consisting of / c.
  • the crystal structure is a hexagonal crystal structure belonging to the space group R-3m or a monoclinic crystal belonging to C2 / m.
  • a crystal structure is particularly preferred.
  • the lithium salt used in the present invention is any one of lithium carbonate, lithium nitrate, lithium sulfate, lithium acetate, lithium hydroxide, lithium oxide, lithium chloride, lithium fluoride, or a mixture of two or more. can do. In these, any one or both of lithium hydroxide and lithium carbonate are preferable.
  • the lithium carbonate component contained in the lithium composite metal oxide is preferably 0.4% by mass or less based on the total mass of the lithium composite metal oxide. More preferably, it is 0.39 mass% or less, and it is especially preferable that it is 0.38 mass% or less.
  • the lithium hydroxide component contained in the lithium composite metal oxide is 0.35% by mass or less based on the total mass of the lithium composite metal oxide.
  • the content is preferably 0.25% by mass or less, and particularly preferably 0.2% by mass or less.
  • the general formula (I) does not include H and C derived from lithium carbonate and lithium hydroxide. This is because lithium carbonate and lithium hydroxide contained in the lithium composite metal oxide are not contained in the crystal structure of the lithium composite metal oxide.
  • Lithium secondary battery> a positive electrode using the positive electrode active material for a lithium secondary battery of the present invention as a positive electrode active material of the lithium secondary battery, and a lithium secondary battery having the positive electrode will be described. To do.
  • An example of the lithium secondary battery of the present embodiment includes a positive electrode and a negative electrode, a separator sandwiched between the positive electrode and the negative electrode, and an electrolytic solution disposed between the positive electrode and the negative electrode.
  • FIG. 1A and 1B are schematic views showing an example of the lithium secondary battery of the present embodiment.
  • the cylindrical lithium secondary battery 10 of this embodiment is manufactured as follows.
  • a pair of separators 1 having a strip shape, a strip-like positive electrode 2 having a positive electrode lead 21 at one end, and a strip-like negative electrode 3 having a negative electrode lead 31 at one end, a separator 1, a positive electrode 2, and a separator 1 and negative electrode 3 are laminated in this order and wound to form electrode group 4.
  • the lithium secondary battery 10 can be manufactured by sealing the upper part of the battery can 5 with the top insulator 7 and the sealing body 8.
  • a columnar shape in which the cross-sectional shape when the electrode group 4 is cut in a direction perpendicular to the winding axis is a circle, an ellipse, a rectangle, or a rectangle with rounded corners. Can be mentioned.
  • a shape of the lithium secondary battery having such an electrode group 4 a shape defined by IEC 60086 or JIS C 8500 which is a standard for a battery defined by the International Electrotechnical Commission (IEC) can be adopted. .
  • IEC 60086 or JIS C 8500 which is a standard for a battery defined by the International Electrotechnical Commission (IEC)
  • cylindrical shape, square shape, etc. can be mentioned.
  • the lithium secondary battery is not limited to the above-described wound type configuration, and may have a stacked type configuration in which a stacked structure of a positive electrode, a separator, a negative electrode, and a separator is repeatedly stacked.
  • Examples of the stacked lithium secondary battery include so-called coin-type batteries, button-type batteries, and paper-type (or sheet-type) batteries.
  • the positive electrode of this embodiment can be manufactured by first adjusting a positive electrode mixture containing a positive electrode active material, a conductive material and a binder, and supporting the positive electrode mixture on a positive electrode current collector.
  • a carbon material As the conductive material included in the positive electrode of the present embodiment, a carbon material can be used.
  • the carbon material include graphite powder, carbon black (for example, acetylene black), and a fibrous carbon material. Since carbon black is fine and has a large surface area, by adding a small amount to the positive electrode mixture, the conductivity inside the positive electrode can be improved and the charge / discharge efficiency and output characteristics can be improved. Both the binding force between the positive electrode mixture and the positive electrode current collector and the binding force inside the positive electrode mixture are reduced, which causes an increase in internal resistance.
  • the proportion of the conductive material in the positive electrode mixture is preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the positive electrode active material.
  • a fibrous carbon material such as graphitized carbon fiber or carbon nanotube is used as the conductive material, this ratio can be lowered.
  • thermoplastic resin As the binder included in the positive electrode of the present embodiment, a thermoplastic resin can be used.
  • the thermoplastic resin include polyvinylidene fluoride (hereinafter sometimes referred to as PVdF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), tetrafluoroethylene, hexafluoropropylene, and vinylidene fluoride.
  • fluororesins such as copolymers, propylene hexafluoride / vinylidene fluoride copolymers, tetrafluoroethylene / perfluorovinyl ether copolymers; polyolefin resins such as polyethylene and polypropylene.
  • thermoplastic resins may be used as a mixture of two or more.
  • a fluororesin and a polyolefin resin as a binder, the ratio of the fluororesin to the total positive electrode mixture is 1% by mass or more and 10% by mass or less, and the ratio of the polyolefin resin is 0.1% by mass or more and 2% by mass or less.
  • a positive electrode mixture having both high adhesion to the current collector and high bonding strength inside the positive electrode mixture can be obtained.
  • a band-shaped member made of a metal material such as Al, Ni, and stainless steel can be used as the positive electrode current collector included in the positive electrode of the present embodiment.
  • a material that is made of Al and formed into a thin film is preferable because it is easy to process and inexpensive.
  • Examples of the method of supporting the positive electrode mixture on the positive electrode current collector include a method of pressure-molding the positive electrode mixture on the positive electrode current collector. Also, the positive electrode mixture is made into a paste using an organic solvent, and the resulting positive electrode mixture paste is applied to at least one surface side of the positive electrode current collector, dried, pressed and fixed, whereby the positive electrode current collector is bonded to the positive electrode current collector. A mixture may be supported.
  • usable organic solvents include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether solvents such as tetrahydrofuran; ketone solvents such as methyl ethyl ketone; methyl acetate And amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine
  • ether solvents such as tetrahydrofuran
  • ketone solvents such as methyl ethyl ketone
  • amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • Examples of the method of applying the positive electrode mixture paste to the positive electrode current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
  • a positive electrode can be manufactured by the method mentioned above.
  • the negative electrode included in the lithium secondary battery of this embodiment is only required to be able to dope and dedope lithium ions at a lower potential than the positive electrode, and the negative electrode mixture containing the negative electrode active material is supported on the negative electrode current collector. And an electrode composed of the negative electrode active material alone.
  • Negative electrode active material examples of the negative electrode active material possessed by the negative electrode include carbon materials, chalcogen compounds (oxides, sulfides, etc.), nitrides, metals, and alloys that can be doped and dedoped with lithium ions at a lower potential than the positive electrode. It is done.
  • Examples of carbon materials that can be used as the negative electrode active material include graphite such as natural graphite and artificial graphite, cokes, carbon black, pyrolytic carbons, carbon fibers, and organic polymer compound fired bodies.
  • the oxide can be used as an anode active material, (wherein, x represents a positive real number) SiO 2, SiO, etc. formula SiO x oxides of silicon represented by; TiO 2, TiO, etc. formula TiO x (wherein , X is a positive real number); oxide of titanium represented by formula VO x (where x is a positive real number) such as V 2 O 5 and VO 2 ; Fe 3 O 4 , Fe 2 O 3 , FeO, etc. Iron oxide represented by the formula FeO x (where x is a positive real number); SnO 2 , SnO, etc.
  • Examples of sulfides that can be used as the negative electrode active material include titanium sulfides represented by the formula TiS x (where x is a positive real number) such as Ti 2 S 3 , TiS 2 , and TiS; V 3 S 4 , VS 2, VS and other vanadium sulfides represented by the formula VS x (where x is a positive real number); Fe 3 S 4 , FeS 2 , FeS and other formulas FeS x (where x is a positive real number) Iron sulfide represented; Mo 2 S 3 , MoS 2 and the like MoS x (where x is a positive real number) Molybdenum sulfide; SnS 2, SnS and other formula SnS x (where, a sulfide of tin represented by x is a positive real number; a sulfide of tungsten represented by a formula WS x (where x is a positive real number) such as WS 2
  • Examples of the nitride that can be used as the negative electrode active material include Li 3 N and Li 3-x A x N (where A is one or both of Ni and Co, and 0 ⁇ x ⁇ 3). And lithium-containing nitrides.
  • These carbon materials, oxides, sulfides and nitrides may be used alone or in combination of two or more. These carbon materials, oxides, sulfides and nitrides may be crystalline or amorphous.
  • examples of the metal that can be used as the negative electrode active material include lithium metal, silicon metal, and tin metal.
  • Alloys that can be used as the negative electrode active material include lithium alloys such as Li—Al, Li—Ni, Li—Si, Li—Sn, and Li—Sn—Ni; silicon alloys such as Si—Zn; Sn—Mn, Sn -Tin alloys such as Co, Sn-Ni, Sn-Cu, Sn-La; alloys such as Cu 2 Sb, La 3 Ni 2 Sn 7 ;
  • These metals and alloys are mainly used alone as electrodes after being processed into a foil shape, for example.
  • carbon materials containing graphite as a main component such as natural graphite and artificial graphite, are preferably used.
  • the shape of the carbon material may be any of a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or an aggregate of fine powder.
  • the negative electrode mixture may contain a binder as necessary.
  • the binder include thermoplastic resins, and specific examples include PVdF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene, and polypropylene.
  • Negative electrode current collector examples of the negative electrode current collector included in the negative electrode include a band-shaped member made of a metal material such as Cu, Ni, and stainless steel. In particular, it is preferable to use Cu as a forming material and process it into a thin film from the viewpoint that it is difficult to make an alloy with lithium and it is easy to process.
  • Examples of the separator included in the lithium secondary battery of the present embodiment include porous films, nonwoven fabrics, and woven fabrics made of materials such as polyolefin resins such as polyethylene and polypropylene, fluororesins, and nitrogen-containing aromatic polymers. A material having the following form can be used. Moreover, a separator may be formed by using two or more of these materials, or a separator may be formed by laminating these materials.
  • the separator allows the electrolyte to permeate well when the battery is used (during charging / discharging). Therefore, the air resistance according to the Gurley method defined in JIS P 8117 is 50 seconds / 100 cc or more, 300 seconds / 100 cc. Or less, more preferably 50 seconds / 100 cc or more and 200 seconds / 100 cc or less.
  • the porosity of the separator is preferably 30% by volume or more and 80% by volume or less, more preferably 40% by volume or more and 70% by volume or less with respect to the volume of the separator.
  • the separator may be a laminate of separators having different porosity.
  • the electrolyte solution included in the lithium secondary battery of this embodiment contains an electrolyte and an organic solvent.
  • the electrolyte contained in the electrolyte includes LiClO 4 , LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 CF 3 ) (COCF 3 ), Li (C 4 F 9 SO 3 ), LiC (SO 2 CF 3 ) 3 , Li 2 B 10 Cl 10 , LiBOB (where BOB is bis (oxalato) borate LiFSI (where FSI is bis (fluorosulfonyl) imide), lower aliphatic carboxylic acid lithium salts, and lithium salts such as LiAlCl 4 , and two or more of these Mixtures may be used.
  • the electrolyte at least selected from the group consisting of LiPF 6 , LiAsF 6 , LiSbF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 and LiC (SO 2 CF 3 ) 3 containing fluorine. It is preferable to use one containing one kind.
  • Examples of the organic solvent contained in the electrolyte include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, and 1,2-di- Carbonates such as (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran, 2- Ethers such as methyltetrahydrofuran; Esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; Nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide, N, N-dimethyla Amides such as toamide; Carbamates such as 3-methyl-2-oxazolidone;
  • a mixed solvent containing carbonates is preferable, and a mixed solvent of cyclic carbonate and acyclic carbonate and a mixed solvent of cyclic carbonate and ethers are more preferable.
  • a mixed solvent of a cyclic carbonate and an acyclic carbonate a mixed solvent containing ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate is preferable.
  • the electrolyte using such a mixed solvent has a wide operating temperature range, hardly deteriorates even when charged and discharged at a high current rate, hardly deteriorates even when used for a long time, and natural graphite as an active material of the negative electrode. Even when a graphite material such as artificial graphite is used, it has many features that it is hardly decomposable.
  • an electrolytic solution containing a lithium salt containing fluorine such as LiPF 6 and an organic solvent having a fluorine substituent because the safety of the obtained lithium secondary battery is increased.
  • a mixed solvent containing ethers having fluorine substituents such as pentafluoropropyl methyl ether and 2,2,3,3-tetrafluoropropyl difluoromethyl ether and dimethyl carbonate is capable of capacity even when charging / discharging at a high current rate. Since the maintenance rate is high, it is more preferable.
  • a solid electrolyte may be used instead of the above electrolytic solution.
  • the solid electrolyte for example, an organic polymer electrolyte such as a polyethylene oxide polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used.
  • maintained the non-aqueous electrolyte in the high molecular compound can also be used.
  • Li 2 S—SiS 2 , Li 2 S—GeS 2 , Li 2 S—P 2 S 5 , Li 2 S—B 2 S 3 , Li 2 S—SiS 2 —Li 3 PO 4 , Li 2 S—SiS 2 -Li 2 SO 4, and an inorganic solid electrolyte can be mentioned include a sulfide such as Li 2 S-GeS 2 -P 2 S 5, it may be used a mixture of two or more thereof. By using these solid electrolytes, the safety of the lithium secondary battery may be further improved.
  • the solid electrolyte when a solid electrolyte is used, the solid electrolyte may serve as a separator, and in that case, the separator may not be required.
  • the positive electrode active material having the above-described configuration uses the above-described lithium-containing composite metal oxide of the present embodiment, the first charge / discharge efficiency of the lithium secondary battery using the positive electrode active material can be improved. .
  • the positive electrode having the above-described configuration has the above-described positive electrode active material for a lithium secondary battery according to the present embodiment, the initial charge / discharge efficiency of the lithium secondary battery can be improved.
  • the lithium secondary battery having the above-described configuration since the lithium secondary battery having the above-described configuration has the positive electrode described above, it becomes a secondary battery with higher initial charge / discharge efficiency than before.
  • Another aspect of the present invention is a method for producing a lithium composite metal oxide containing at least nickel, the first cleaning step of cleaning the lithium composite metal oxide with a first cleaning liquid, and the first cleaning step.
  • a second washing step of washing the washed product with a second washing liquid wherein the first washing liquid and the second washing liquid are alkaline washing liquids each containing a compound containing an alkali metal,
  • the concentration of the alkali metal in the first cleaning liquid with respect to the total mass of the first cleaning liquid is 10% by mass to 20% by mass, and the alkali metal in the second cleaning liquid with respect to the total mass of the second cleaning liquid
  • the concentration is 2% by mass or more and 10% by mass or less, and the concentration of the alkali metal in the first cleaning liquid with respect to the total mass of the first cleaning liquid is the second cleaning with respect to the total mass of the second cleaning liquid. Higher than the concentration of the alkali metal in a method for producing a lithium mixed metal oxide.
  • At least one of the alkali metal-containing compounds contained in the first cleaning liquid and the second cleaning liquid is lithium hydroxide.
  • the alkali metal-containing compound contained in the first cleaning liquid and the second cleaning liquid is lithium hydroxide.
  • Another aspect of the present invention is a method for producing a lithium composite metal oxide containing at least nickel, the first cleaning step of cleaning the lithium composite metal oxide with a first cleaning liquid, and the first cleaning step.
  • a second washing step of washing the washed product with a second washing liquid wherein the first washing liquid and the second washing liquid are alkaline washing liquids each containing a compound containing an alkali metal,
  • the concentration of alkali metal in the first cleaning liquid with respect to the total mass of the first cleaning liquid is 2.5 to 20 times the concentration of alkali metal in the second cleaning liquid with respect to the total mass of the second cleaning liquid.
  • a method for producing a lithium composite metal oxide is a method for producing a lithium composite metal oxide.
  • At least one of the alkali metal-containing compounds contained in the first cleaning liquid and the second cleaning liquid is lithium hydroxide.
  • the alkali metal-containing compound contained in the first cleaning liquid and the second cleaning liquid is lithium hydroxide.
  • Another aspect of the present invention is a lithium secondary battery positive electrode containing a lithium composite metal oxide as a positive electrode active material, a separator on the lithium secondary battery positive electrode, and a lithium secondary battery negative electrode on the separator.
  • evaluation of the lithium composite metal oxide and production evaluation of the positive electrode for the lithium secondary battery and the lithium secondary battery were performed as follows.
  • composition analysis of the lithium composite metal oxide powder produced by the method described below is carried out by dissolving the obtained lithium composite metal oxide powder in hydrochloric acid and then using an inductively coupled plasma emission spectrometer (SII Nanotechnology Co., Ltd.). Manufactured by SPS3000).
  • N-methyl-2-pyrrolidone was used as the organic solvent.
  • the obtained positive electrode mixture was applied to an Al foil having a thickness of 40 ⁇ m serving as a current collector and vacuum-dried at 150 ° C. for 8 hours to obtain a positive electrode for a lithium secondary battery.
  • the electrode area of the positive electrode for the lithium secondary battery was 1.65 cm 2 .
  • the obtained negative electrode mixture was applied to a 12 ⁇ m thick Cu foil serving as a current collector and vacuum dried at 60 ° C. for 8 hours to obtain a negative electrode for a lithium secondary battery.
  • the electrode area of the negative electrode for a lithium secondary battery was 1.77 cm 2 .
  • the electrolytic solution was ethylene carbonate (hereinafter sometimes referred to as EC), dimethyl carbonate (hereinafter sometimes referred to as DMC), and ethyl methyl carbonate (hereinafter sometimes referred to as EMC) 30:35. : 35 (volume ratio) a mixture of LiPF 6 dissolved to 1.0 mol / l (hereinafter sometimes referred to as LiPF 6 / EC + DMC + EMC) was used.
  • LiPF 6 / EC + DMC + EMC lithium metal as the negative electrode
  • the negative electrode is placed on the upper side of the laminated film separator, covered with a gasket, and then caulked with a caulking machine to form a lithium secondary battery (coin type half cell R2032, hereinafter "half cell”).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • Test temperature 25 ° C Maximum charging voltage 4.3V, charging time 6 hours, charging current 0.2CA, constant current constant voltage charging Minimum discharging voltage 2.5V, discharging time 5 hours, discharging current 0.2CA, constant current discharging
  • the initial charge / discharge efficiency is obtained from the following equation. ⁇ First charge / discharge efficiency (%)> (Initial discharge capacity [mAh / g]) ⁇ (Initial charge capacity [mAh / g]) ⁇ 100
  • Example 1 Production of Lithium Composite Metal Oxide 1 After water was placed in a reaction vessel equipped with a stirrer and an overflow pipe, an aqueous sodium hydroxide solution was added to keep the liquid temperature at 50 ° C.
  • a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution, a manganese sulfate aqueous solution, and an aluminum sulfate aqueous solution have an atomic ratio of nickel atom, cobalt atom, manganese atom, and aluminum atom of 87.5: 9.5: 2.0: 1.0. It mixed so that the mixed raw material liquid might be prepared.
  • the mixed raw material solution and the aqueous ammonium sulfate solution were continuously added as a complexing agent to the reaction vessel, and nitrogen gas was continuously passed through.
  • a sodium hydroxide aqueous solution was dropped in a timely manner so that the pH of the solution in the reaction vessel measured at 40 ° C. was 11.0 to obtain a nickel cobalt manganese aluminum composite hydroxide, washed with the sodium hydroxide aqueous solution, and then centrifuged. By dehydrating and isolating with a separator, and drying at 105 ° C., nickel cobalt manganese aluminum composite hydroxide was obtained.
  • a lithium hydroxide aqueous solution in which tungsten oxide was dissolved was prepared.
  • the concentration of tungsten oxide in the prepared tungsten-dissolved lithium hydroxide aqueous solution was 61 g / L.
  • the concentration of lithium hydroxide in the tungsten-dissolved lithium hydroxide aqueous solution was 66.6 g / L.
  • Example 2 Production of lithium composite metal oxide 2 Lithium composite metal oxide 2 was prepared in the same manner as in Example 1 except that the first cleaning step and the second cleaning step were performed using the cleaning liquid shown in Table 1 below. Manufactured.
  • Lithium composite metal oxide 3 was prepared in the same manner as in Example 1 except that the first cleaning step and the second cleaning step were performed using the cleaning liquid shown in Table 1 below. Manufactured.
  • Lithium composite metal oxide 4 was produced in the same manner as in Example 1 except that the first cleaning step and the second cleaning step were performed using the cleaning liquid shown in Table 1 below. Manufactured.
  • Lithium composite metal oxide 5 was prepared in the same manner as in Example 1 except that the first cleaning step and the second cleaning step were performed using the cleaning liquid shown in Table 1 below. Manufactured.
  • Examples 1 and 2 in which the cleaning process to which the present invention was applied had higher initial charge / discharge efficiency than Comparative Examples 1 to 3 to which the present invention was not applied. This is because when the present invention is applied, the elution of lithium from the lithium composite metal oxide is small and the concentration gradient of lithium on the surface of the lithium composite metal oxide is small compared to the case of washing with pure water. Can be considered.
  • a method for producing a lithium composite metal oxide having high initial charge / discharge efficiency can be provided.

Landscapes

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

Abstract

Ce procédé de production d'oxyde métallique composite de lithium est destiné à produire un oxyde métallique composite de lithium contenant au moins du nickel, et comprend : une première étape de lavage pour laver un oxyde métallique composite de lithium à l'aide d'un premier liquide de lavage ; et une seconde étape de lavage pour laver le produit lavé, obtenu à l'issue de la première étape de lavage, à l'aide d'un second liquide de lavage, le premier liquide de lavage étant un liquide de lavage alcalin contenant un composé contenant des métaux alcalins, le second liquide de lavage étant un liquide de lavage alcalin contenant un composé contenant des métaux alcalins et/ou un composé alcalin ne contenant pas de métaux alcalins, et la concentration en métaux alcalins du premier liquide de lavage par rapport à la masse totale du premier liquide de lavage est supérieure à la concentration en métaux alcalins du second liquide de lavage par rapport à la masse totale du second liquide de lavage.
PCT/JP2018/012725 2017-03-31 2018-03-28 Procédé de production d'oxyde métallique composite de lithium WO2018181465A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020197024218A KR102545342B1 (ko) 2017-03-31 2018-03-28 리튬 복합 금속 산화물의 제조 방법
CN201880014933.2A CN110366541B (zh) 2017-03-31 2018-03-28 锂复合金属氧化物的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017-072870 2017-03-31
JP2017072870A JP6937152B2 (ja) 2017-03-31 2017-03-31 リチウム複合金属酸化物の製造方法

Publications (1)

Publication Number Publication Date
WO2018181465A1 true WO2018181465A1 (fr) 2018-10-04

Family

ID=63676214

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/012725 WO2018181465A1 (fr) 2017-03-31 2018-03-28 Procédé de production d'oxyde métallique composite de lithium

Country Status (4)

Country Link
JP (1) JP6937152B2 (fr)
KR (1) KR102545342B1 (fr)
CN (1) CN110366541B (fr)
WO (1) WO2018181465A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114365307A (zh) * 2019-06-13 2022-04-15 坚能创智有限公司 二次电池的阴极的制备方法
EP4089053A4 (fr) * 2020-04-17 2023-08-02 Lg Chem, Ltd. Procédé de préparation de matériau actif de cathode

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102165119B1 (ko) * 2017-10-20 2020-10-14 주식회사 엘지화학 이차전지용 양극활물질 제조방법 및 이를 이용하는 이차전지
JP7404886B2 (ja) * 2019-03-15 2023-12-26 株式会社豊田自動織機 層状岩塩構造を示し、リチウム、ニッケル、コバルト、タングステン、アルミニウム及び酸素を含有する正極活物質、並びに、その製造方法
CN113258130B (zh) * 2021-04-27 2023-01-03 燕山大学 非晶卤化物固体电解质及制备和在全固态电池中的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004273451A (ja) * 2003-02-21 2004-09-30 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および非水系電解質二次電池
JP2015144131A (ja) * 2010-07-20 2015-08-06 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物およびその製造方法
WO2016060105A1 (fr) * 2014-10-15 2016-04-21 住友化学株式会社 Matière active d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2016104488A1 (fr) * 2014-12-25 2016-06-30 住友化学株式会社 Matériau actif d'électrode positive pour batteries rechargeables au lithium, électrode positive pour batteries rechargeables au lithium, et batterie rechargeable au lithium

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004265806A (ja) 2003-03-04 2004-09-24 Canon Inc リチウム金属複合酸化物粒子、前記リチウム金属複合酸化物粒子の製造方法、前記リチウム金属複合酸化物粒子を含有す電極構造体、前記電極構造体の製造方法、及び前記電極構造体を有するリチウム二次電池
JP4595475B2 (ja) 2004-10-01 2010-12-08 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質およびこれを用いた非水系電解質二次電池およびその製造方法
JP4789066B2 (ja) 2006-03-06 2011-10-05 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質及びその製造方法
JP5214202B2 (ja) * 2007-09-21 2013-06-19 パナソニック株式会社 非水電解質二次電池およびその製造方法
JP2011057518A (ja) * 2009-09-11 2011-03-24 Kansai Shokubai Kagaku Kk 高密度ニッケル・コバルト・マンガン共沈水酸化物及びその製造方法
JP2011134551A (ja) * 2009-12-24 2011-07-07 Sumitomo Chemical Co Ltd 電極活物質、電極およびナトリウム二次電池
KR101375623B1 (ko) * 2012-02-28 2014-03-18 비나텍주식회사 슈퍼커패시터 전극의 제조방법
US9583763B2 (en) * 2012-07-06 2017-02-28 Sumitomo Chemical Company, Limited Lithium composite metal oxide, positive electrode active substance, positive electrode, and non-aqueous electrolyte secondary battery
WO2015008582A1 (fr) * 2013-07-17 2015-01-22 住友金属鉱山株式会社 Matériau actif d'électrode positive pour accumulateur à électrolyte non aqueux, procédé de production dudit matériau actif d'électrode positive pour accumulateur à électrolyte non aqueux, et accumulateur à électrolyte non aqueux utilisant ledit matériau actif d'électrode positive pour accumulateur à électrolyte non aqueux
JP2015122264A (ja) * 2013-12-25 2015-07-02 トヨタ自動車株式会社 非水電解液二次電池の製造方法
CN104091942B (zh) * 2014-07-07 2016-06-29 中南大学 控制层状高镍正极材料表面残锂的方法
JP6319632B2 (ja) * 2014-07-23 2018-05-09 株式会社豊田自動織機 リチウムイオン二次電池用正極とその製造方法及びリチウムイオン二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004273451A (ja) * 2003-02-21 2004-09-30 Sumitomo Metal Mining Co Ltd 非水系電解質二次電池用正極活物質および非水系電解質二次電池
JP2015144131A (ja) * 2010-07-20 2015-08-06 国立研究開発法人産業技術総合研究所 リチウムマンガン系複合酸化物およびその製造方法
WO2016060105A1 (fr) * 2014-10-15 2016-04-21 住友化学株式会社 Matière active d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2016104488A1 (fr) * 2014-12-25 2016-06-30 住友化学株式会社 Matériau actif d'électrode positive pour batteries rechargeables au lithium, électrode positive pour batteries rechargeables au lithium, et batterie rechargeable au lithium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114365307A (zh) * 2019-06-13 2022-04-15 坚能创智有限公司 二次电池的阴极的制备方法
CN114365307B (zh) * 2019-06-13 2023-10-13 坚能创智有限公司 二次电池的阴极的制备方法
EP4089053A4 (fr) * 2020-04-17 2023-08-02 Lg Chem, Ltd. Procédé de préparation de matériau actif de cathode

Also Published As

Publication number Publication date
KR20190127683A (ko) 2019-11-13
KR102545342B1 (ko) 2023-06-19
JP6937152B2 (ja) 2021-09-22
CN110366541B (zh) 2022-01-18
JP2018172256A (ja) 2018-11-08
CN110366541A (zh) 2019-10-22

Similar Documents

Publication Publication Date Title
JP6495997B1 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6337360B2 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6256956B1 (ja) リチウム金属複合酸化物粉末、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6368022B1 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2016060105A1 (fr) Matière active d'électrode positive pour batterie secondaire au lithium, électrode positive pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2019187953A1 (fr) Composé métallique composite de lithium, matériau actif d'électrode positive de batterie secondaire au lithium, électrode positive de batterie secondaire au lithium, batterie secondaire au lithium et procédé de production de composé métallique composite de lithium
WO2018181530A1 (fr) Procédé de production d'un oxyde complexe de métal de lithium
WO2018079816A1 (fr) Précurseur de matière active d'électrode positive pour batterie secondaire au lithium, et procédé de fabrication de matière active d'électrode positive pour batterie secondaire au lithium
JP6388978B1 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2018181402A1 (fr) Procédé de production d'oxyde composite de lithium-nickel
JP6500001B2 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
WO2018181465A1 (fr) Procédé de production d'oxyde métallique composite de lithium
WO2017078136A1 (fr) Matériau actif d'électrode positive pour des batteries secondaires au lithium, procédé de production d'un matériau actif d'électrode positive pour des batteries secondaires au lithium, électrode positive pour des batteries secondaires au lithium, et batterie secondaire au lithium
WO2019168091A1 (fr) Oxyde composite lithium-métal, matériau actif d'électrode positive d'accumulateur au lithium, électrode positive et accumulateur au lithium
JP2018081937A (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP2018174161A (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP2018098217A (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6360374B2 (ja) リチウム含有複合金属酸化物の製造方法
JP2018095546A (ja) リチウム金属複合酸化物粉末、リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池
JP6381606B2 (ja) リチウム二次電池用正極活物質、リチウム二次電池用正極及びリチウム二次電池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18775743

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20197024218

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18775743

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载