WO2015186321A1 - Matériau possédant une partie d'oxyde métallique composite de lithium et une partie contenant du bore et son procédé de production - Google Patents

Matériau possédant une partie d'oxyde métallique composite de lithium et une partie contenant du bore et son procédé de production Download PDF

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WO2015186321A1
WO2015186321A1 PCT/JP2015/002712 JP2015002712W WO2015186321A1 WO 2015186321 A1 WO2015186321 A1 WO 2015186321A1 JP 2015002712 W JP2015002712 W JP 2015002712W WO 2015186321 A1 WO2015186321 A1 WO 2015186321A1
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metal oxide
composite metal
lithium composite
boron
lithium
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PCT/JP2015/002712
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English (en)
Japanese (ja)
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潤 齊田
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株式会社豊田自動織機
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Priority to JP2016525682A priority Critical patent/JP6296156B2/ja
Publication of WO2015186321A1 publication Critical patent/WO2015186321A1/fr

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    • 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
    • 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 material having a lithium composite metal oxide part and a boron-containing part and a method for producing the same.
  • Li a Ni b Co c Mn d De O f (0.2 ⁇ a ⁇ 2, b + c + d + e 1, 0 ⁇ e ⁇ 1, D is Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo At least one element selected from Nb, W, La, Hf, and Rf, 1.7 ⁇ f ⁇ 3) is widely used as an active material for lithium ion secondary batteries. .
  • Patent Document 1 describes an active material in which a lithium composite metal oxide is immersed in a boron ethoxide solution and heated at 100 ° C. (Examples 11 to 17), and lithium ions using the active material are described. It is described that a secondary battery is suitable.
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a new material that can be an active material.
  • the present inventor thought that with the technique disclosed in Patent Document 1, the boron compound may not have sufficiently covered the lithium composite metal oxide. Therefore, the present inventor has devised a technique in which a boron compound uniformly coats a lithium composite metal oxide using a boron compound solution. As a result of further intensive studies by the inventor on the technology, the inventors have found that a new material that can be an excellent active material can be obtained by heating in a specific temperature range, and the present invention has been completed.
  • the present invention can provide a new material that can be an active material.
  • FIG. 1 is a SEM photograph of the material of Example 1.
  • 4 is an ABF-STEM image of a cross section of primary particles of the material of Example 2.
  • the numerical range “x to y” described in this specification includes the lower limit x and the upper limit y.
  • the numerical range can be configured by arbitrarily combining these upper limit value and lower limit value and the numerical values listed in the examples.
  • numerical values arbitrarily selected from the numerical value range can be used as upper and lower numerical values.
  • Li a Ni b Co c Mn d De O f (0.2 ⁇ a ⁇ 2, b + c + d + e 1, 0 ⁇ e ⁇ 1, D is Fe, Cr, Cu, Zn, Ca, Mg, Zr, In at least one element selected from S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf, and Rf (1.7 ⁇ f ⁇ 3), b , C, and d are not particularly limited as long as the above conditions are satisfied, but 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1 is preferable, and b, Preferably, at least one of c and d is in the range of 10/100 ⁇ b ⁇ 90/100, 10/100 ⁇ c ⁇ 90/100, 5/100 ⁇ d ⁇ 70/100, and 12/100 ⁇ b ⁇ 80/100, 12/100 ⁇ c ⁇ 80/
  • a, e, f may be any numerical value within the range defined by the general formula, and preferably 0.5 ⁇ a ⁇ 1.5, 0 ⁇ e ⁇ 0.2, 1.8 ⁇ f ⁇ 2.5 More preferably, 0.8 ⁇ a ⁇ 1.3, 0 ⁇ e ⁇ 0.1, 1.9 ⁇ f ⁇ 2.1 can be exemplified.
  • the lithium composite metal oxide may be commercially available.
  • the lithium composite metal oxide may be manufactured according to a conventional well-known manufacturing method using a metal salt such as a metal oxide, a metal hydroxide, or a metal carbonate.
  • the said lithium complex metal oxide is manufactured by baking a precursor at 750 degreeC or more, for example, and arrangement
  • the lithium composite metal oxide can be manufactured as follows (coprecipitation method).
  • a sulfuric acid aqueous solution containing nickel sulfate, cobalt sulfate and manganese sulfate in predetermined amounts is made alkaline to obtain a coprecipitation slurry, which is dried to obtain a nickel cobalt manganese composite hydroxide.
  • a predetermined amount of lithium carbonate is mixed with nickel cobalt manganese composite hydroxide and baked at 750 ° C. or higher to obtain a lithium composite metal oxide having a layered rock salt structure.
  • the firing may be a multi-stage method in which firing is performed at a plurality of temperature conditions.
  • the obtained lithium composite metal oxide may be appropriately pulverized to be powdered, and further classified to a desired particle size.
  • the average particle size (D50) is preferably 100 ⁇ m or less, more preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more, as measured with a general laser scattering diffraction type particle size distribution meter. It is more preferably 30 ⁇ m or less, and particularly preferably 2 ⁇ m or more and 20 ⁇ m or less.
  • the lithium composite metal oxide is a solid phase method or spray dry method for a mixed raw material comprising a lithium raw material containing Li and a metal raw material containing one or more selected from Ni, Mn, and Co. It can be produced using a known method such as a hydrothermal method or a molten salt method.
  • the solid phase method is a method of obtaining a lithium composite metal oxide by mixing and pulverizing mixed raw material powder, drying and compacting as necessary, and heating and firing.
  • each raw material is mixed in a proportion corresponding to the composition of the lithium composite metal oxide to be produced.
  • the heating temperature of the raw material mixture in the solid phase method is preferably 900 ° C. or higher and 1000 ° C. or lower, and the heating time is preferably 8 hours or longer and 24 hours or shorter.
  • the spray drying method is a method in which powder of a mixed raw material is dissolved in a liquid to form a solution, and the solution is sprayed into the air to form a mist, and the mist solution is heated. In the spray drying method, further heating may be performed later.
  • the heating temperature in the spray drying method is preferably 500 ° C. or more and 1000 ° C. or less, and the heating time is preferably 3 hours or more and 8 hours or less.
  • the hydrothermal method is a method in which a raw material is mixed with water to form a mixed solution, and the mixed solution is heated under high temperature and high pressure.
  • the heating temperature in the hydrothermal method is preferably from 120 ° C. to 200 ° C., and the heating time is preferably from 2 hours to 24 hours.
  • the molten salt method is a method in which a lithium compound is heated to melt into a molten salt by heating a raw material mixture containing a lithium compound, and a lithium composite metal oxide is synthesized in the molten liquid.
  • the molar ratio of Li of the lithium composite metal oxide to be manufactured should be less than 1 with respect to Li of the lithium compound.
  • the ratio is preferably less than 0.7 and more preferably 0.03 to 0.5 and 0.04 to 0.25.
  • D in the above general formula is a doping element.
  • the doping element-containing compound may be added at any stage of producing the lithium composite metal oxide. . What is necessary is just to determine the compounding quantity of a dope element containing compound suitably so that it may become a desired dope amount.
  • Step b) is a step of preparing a dispersion in which the lithium composite metal oxide is dispersed in a boron compound solution.
  • boron compound may be used as long as it contains boron.
  • boric acid derivatives such as H 3 BO 3 , H 3 BO, LiBO 2 , Li 2 B 4 O 7 , LiB 5 O 8 , HBO 2, and the like Boron oxide such as salt, B 2 O 3 , BO, B 2 O 2 , B 4 O 5 , B 6 O, B 7 O, B 13 O 2 , BH 3 , NaBH 4 , LiBF 4 , BF 3 , BaB 6 , CeB 6 , Co 2 B, CoB, FeB, GdB 4 , GdB 6 , LaB 4 , LaB 6 , Mo 2 B, MoB, MoB 2 , Mo 2 B 5 , Nb 3 B 2 , NbB, Nb 3 B 4 , NbB 2, NbB 4, NbB 6 , PrB 4, PrB 6, SrB 6, TaB, TaB 2, TiB, TiB 2, VB, VB 2, W 2 B 5, YB 4, YB 6,
  • the boron compounds that have particularly high conductivity and contribute to lowering the resistance of the material of the present invention include BaB 6 , FeB, GdB 4 , GdB 6 , LaB 4 , LaB 6 , MoB 2 , Mo 2 B 5 , Nb 3 B 2 , NbB, Nb 3 B 4 , NbB 2 , PrB 4 , PrB 6 , SrB 6 , TaB, TaB 2 , TiB, TiB 2 , VB, VB 2 , W 2 B 5 , YB 4 , YB 6 , YB 12 , ZrB 2 can be exemplified.
  • boron compounds that have high acid resistance and contribute to the improvement of the capacity retention rate of the secondary battery including the material of the present invention include LaB 6 , MoB, TiB 2 , VB 2 , Examples thereof include NbB 2 , TaB 2 , ZrB 2 , CrB, CrB 2 , WB, and HfB 2 .
  • the step may be performed by adding a boron compound to the lithium composite metal oxide dispersion, or may be performed by adding a lithium composite metal oxide to the boron compound solution.
  • the amount of the boron compound dissolved in the dispersion in step b) is preferably an amount that is close to the saturation solubility in the dispersion, or may be an amount that is supersaturated in the dispersion.
  • the step b) is preferably carried out under stirring conditions, and is preferably carried out under warming conditions within the range of 30 to 60 ° C., preferably 35 to 50 ° C.
  • the solvent for the dispersion liquid examples include water, alcohols such as methanol and ethanol, and polar organic solvents such as tetrahydrofuran.
  • the solvent for the dispersion liquid examples include water, alcohols such as methanol and ethanol, and polar organic solvents such as tetrahydrofuran.
  • the above-mentioned solvents may be employed alone or in combination.
  • the pH of the dispersion solvent may be controlled with an acid or a base.
  • Step c) is a step of lowering the liquid temperature of the dispersion obtained in step b) and attaching a boron compound to the surface of the lithium composite metal oxide.
  • the step c) is basically a step utilizing the difference in solubility of the boron compound for each temperature in the dispersion.
  • the dispersion liquid may be gradually cooled using a cooling device, or rapidly cooled using an ice bath or a cooling device. Good. Further, for example, if the dispersion liquid in step b) is at a high temperature, it may be left until it reaches room temperature. In order to uniformly deposit the boron compound on the surface of the lithium composite metal oxide, a method of gradually cooling the dispersion is preferable. When the dispersion is rapidly cooled at a remarkable rate, boron compound crystal nuclei are suddenly generated everywhere in the dispersion, and the boron compound crystals may grow. It may be difficult to deposit the compound uniformly.
  • the boron compound attached to the surface of the lithium composite metal oxide in step c) is not necessarily the same as the boron compound used in step b). Absent.
  • the boron compound employed in step b) is decomposed in the dispersion to form another boron compound, and may adhere to the surface of the lithium composite metal oxide in step c).
  • step C) The step is preferably performed under stirring conditions.
  • step c) may be performed while removing the solvent of the dispersion under reduced pressure. Precipitation of a boron compound may be promoted by making it under stirring conditions and / or reduced pressure conditions.
  • the lithium composite metal oxide having a boron compound attached to the surface can be separated by filtration or the like.
  • the lithium composite metal oxide after separation is preferably subjected to a washing step in which the lithium composite metal oxide is washed with a solvent such as water or alcohol.
  • a solvent such as water or alcohol.
  • water distilled water, reverse osmosis membrane permeated water, or deionized water is preferable.
  • the boron compound excessively attached to the surface of the lithium composite metal oxide can be removed.
  • the solvent for the washing step a single solvent may be used, or a mixed solvent of a plurality of solvents may be used.
  • the washing process may be repeated a plurality of times. In that case, the solvent may be changed.
  • the lithium composite metal oxide after separation is preferably dried to remove the solvent. *
  • Step d) is a step of heating the lithium composite metal oxide that has undergone step c) at a temperature of 400 ° C. or higher.
  • a lithium composite metal oxide having a boron compound attached to the surface at 400 ° C. or higher boron and Ni, Co, or Mn contained in the lithium composite metal oxide are bonded to each other to form a B—Ni bond, B— A boron-containing portion having a Co bond or a B—Mn bond can be formed.
  • the process should just have the process heated at 400 degreeC or more.
  • 600 degreeC and 700 degreeC can be illustrated.
  • the temperature range is preferably 400 ° C. to 700 ° C., more preferably 415 ° C. to 600 ° C., further preferably 420 ° C. to 550 ° C., and still more preferably 430 ° C. to 520 ° C.
  • the range of 450 ° C. to 500 ° C. is particularly preferable, and the range of 460 ° C. to 490 ° C. is most preferable.
  • the heating time at 400 ° C. or higher is preferably 1 to 20 hours, more preferably 3 to 10 hours.
  • the heating temperature in step d) is preferably 417 ° C. or higher.
  • an alloy recognized as Ni 2 B shows a decrease in resistance near 490 ° C. and DTA It is described that the crystallization start temperature was confirmed around 440 to 470 ° C. by measurement. From the description of the document, with the crystallization of Ni 2 B, it can be said that the resistance of the Ni 2 B is lowered. From this point, it can be said that the heating temperature in step d) is preferably 440 ° C. or higher.
  • preliminary heating may be performed at 200 ° C. or higher and lower than 400 ° C.
  • the metal composition in the vicinity of the surface of the lithium composite metal oxide can be changed, and as a result, the bonding between boron and a desired metal is preferentially caused by subsequent heating at 400 ° C. or higher. be able to.
  • the preheating temperature range is preferably 250 ° C. to 390 ° C., more preferably 300 ° C. to 380 ° C.
  • the preheating time is preferably 1 to 20 hours, and more preferably 3 to 10 hours.
  • step d) may be performed under a temperature increase rate control that gradually raises the temperature from room temperature to a low temperature of about 100 ° C. to 400 ° C. or higher.
  • a temperature raising program that sufficiently performs preheating or a temperature raising program that hardly performs preheating may be used.
  • step D) may be performed under atmospheric conditions, may be performed in the presence of an inert gas such as helium or argon, or may be performed in a nitrogen gas atmosphere.
  • step d) is preferably performed under atmospheric conditions.
  • conductive nitride is generated in the boron-containing portion, which may be a more suitable material.
  • boron-containing portion either a B—Ni bond, a B—Co bond, or a B—Mn bond exists.
  • Conductive NiB, CoB, Co 2 B, MnB 2, and the like are generated at locations showing B—Ni bonds, B—Co bonds, and B—Mn bonds, respectively, in the boron-containing portion. Due to the presence of these conductive substances, the material of the present invention may exhibit suitable conductivity.
  • a boron compound itself or a material derived from a boron compound may exist.
  • the electrical conductivity of NiB, CoB, Co 2 B, and MnB 2 is shown in Table 1.
  • the boron-containing portion is preferably present on the surface layer in the range of 50 nm from the surface of the material of the present invention to the inside, more preferably in the surface layer in the range of 30 nm, and in the surface layer in the range of 20 nm. More preferably.
  • Boron-containing portions may be scattered or may be present as a layer.
  • the boron-containing part is preferably present on the entire surface of the material of the present invention.
  • the thickness t (nm) of the boron-containing portion layer is, for example, 0 ⁇ t ⁇ 30, preferably 0.01 ⁇ t ⁇ 20, and more preferably 0.1 ⁇ t ⁇ 10.
  • the material of the present invention obtained through the step is preferably powdered by pulverization, and more preferably classified into an appropriate range of particle size using a sieve or the like.
  • the average particle diameter (D50) is preferably 100 ⁇ m or less, more preferably 1 ⁇ m or more and 50 ⁇ m or less, and more preferably 1 ⁇ m or more and 30 ⁇ m in the measurement with a general laser scattering diffraction type particle size distribution meter. The following is more preferable, and 2 ⁇ m or more and 20 ⁇ m or less is particularly preferable.
  • the size of the primary particles of the material of the present invention is preferably within the range of 50 nm to 1500 nm by microscopic observation.
  • the material of the present invention is preferably subjected to a washing process in which the material is washed with a solvent such as water or alcohol.
  • a solvent such as water or alcohol.
  • water distilled water, reverse osmosis membrane permeated water, or deionized water is preferable.
  • the washing step can remove excessive boron-containing materials and other unnecessary materials from the surface of the material of the present invention.
  • a single solvent may be used, or a mixed solvent of a plurality of solvents may be used.
  • the washing process may be repeated a plurality of times. In that case, the solvent may be changed.
  • the washed material of the present invention is preferably dried to remove the solvent.
  • the material of the present invention can be used as an active material of a lithium ion secondary battery.
  • the lithium ion secondary battery of the present invention comprises the material of the present invention as an active material.
  • the lithium ion secondary battery of the present invention includes a positive electrode, a negative electrode, an electrolytic solution, and a separator that include the material of the present invention as an active material.
  • a boron-containing portion is formed on the surface of the lithium composite metal oxide. Due to the presence of the boron-containing portion, in the positive electrode including the material of the present invention as an active material, it is possible to suppress the elution of the transition metal constituting the lithium composite metal oxide from the positive electrode to some extent.
  • the positive electrode has a current collector and a positive electrode active material layer bound to the surface of the current collector.
  • the current collector refers to a chemically inert electronic conductor that keeps a current flowing through an electrode during discharge or charging of a lithium ion secondary battery.
  • As the current collector at least one selected from silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium, titanium, ruthenium, tantalum, chromium, molybdenum, and stainless steel, etc. Metal materials can be exemplified.
  • the current collector may be covered with a known protective layer. What collected the surface of the electrical power collector by the well-known method may be used as an electrical power collector.
  • the current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.
  • the thickness is preferably in the range of 1 ⁇ m to 100 ⁇ m.
  • the positive electrode active material layer contains a positive electrode active material and, if necessary, a conductive additive and / or a binder.
  • any material containing the material of the present invention may be used, and only the material of the present invention may be adopted, or the material of the present invention and a known positive electrode active material may be used in combination.
  • Conductive aid is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent.
  • the conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, acetylene black, ketjen black (registered trademark), or vapor grown carbon fiber (Vapor Grown Carbon). Fiber: VGCF) and various metal particles are exemplified. These conductive assistants can be added to the active material layer alone or in combination of two or more.
  • the binder serves to hold the active material and the conductive auxiliary agent on the surface of the current collector and maintain the conductive network in the electrode.
  • the binder include fluorine-containing resins such as polyvinylidene fluoride, polytetrafluoroethylene, and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide resins such as polyimide and polyamideimide, alkoxysilyl group-containing resins, poly ( Examples thereof include acrylic resins such as (meth) acrylic acid, styrene-butadiene rubber (SBR), and carboxymethylcellulose. These binders may be used singly or in plural.
  • the negative electrode has a current collector and a negative electrode active material layer bound to the surface of the current collector. What is necessary is just to employ
  • the negative electrode active material layer includes a negative electrode active material and, if necessary, a conductive additive and / or a binder.
  • Examples of the negative electrode active material include a carbon-based material capable of inserting and extracting lithium, an element that can be alloyed with lithium, a compound having an element that can be alloyed with lithium, a polymer material, and the like.
  • the carbon-based material examples include non-graphitizable carbon, graphite, coke, graphite, glassy carbon, organic polymer compound fired body, carbon fiber, activated carbon, or carbon black.
  • the organic polymer compound fired body refers to a material obtained by firing and carbonizing a polymer material such as phenols and furans at an appropriate temperature.
  • elements that can be alloyed with lithium include Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Ti, Ag, Zn, Cd, Al, Ga, In, Si. , Ge, Sn, Pb, Sb, Bi can be exemplified, and Si or Sn is particularly preferable.
  • Specific examples of compounds having elements that can be alloyed with lithium include ZnLiAl, AlSb, SiB 4 , SiB 6 , Mg 2 Si, Mg 2 Sn, Ni 2 Si, TiSi 2 , MoSi 2 , CoSi 2 , NiSi 2 , CaSi 2, CrSi 2, Cu 5 Si, FeSi 2, MnSi 2, NbSi 2, TaSi 2, VSi 2, WSi 2, ZnSi 2, SiC, Si 3 N 4, Si 2 N 2 O, SiO v (0 ⁇ v ⁇ 2), SnO w (0 ⁇ w ⁇ 2), SnSiO 3 , LiSiO 2 or LiSnO, particularly SiO x (0.3 ⁇ x ⁇ 1.6, or 0.5 ⁇ x ⁇ 1.5) Is preferred.
  • the negative electrode active material preferably includes a Si-based material having Si.
  • the Si-based material may be made of silicon or / and a silicon compound capable of occluding / releasing lithium ions, for example, SiOx (0.5 ⁇ x ⁇ 1.5).
  • SiOx 0.5 ⁇ x ⁇ 1.5
  • silicon has a large theoretical charge / discharge capacity
  • silicon has a large volume change during charge / discharge. Therefore, the volume change of silicon can be mitigated by using SiOx containing silicon as the negative electrode active material.
  • the Si-based material preferably has a Si phase and a SiO 2 phase.
  • the Si phase is composed of simple silicon, and is a phase that can occlude and release Li ions, and expands and contracts as Li ions are occluded and released.
  • the SiO 2 phase is made of SiO 2 and serves as a buffer phase that absorbs the expansion and contraction of the Si phase.
  • a Si-based material in which the Si phase is covered with the SiO 2 phase is preferable.
  • it is preferable that a plurality of micronized Si phases are covered with a SiO 2 phase to form particles integrally. In this case, the volume change of the entire Si-based material can be effectively suppressed.
  • the mass ratio of the SiO 2 phase to the Si phase in the Si-based material is preferably 1 to 3.
  • the mass ratio is less than 1, the expansion and contraction of the Si-based material increases, and the negative electrode active material layer containing the Si-based material may be cracked.
  • the mass ratio exceeds 3, the amount of occlusion and release of Li ions of the negative electrode active material decreases, and the electric capacity per unit negative electrode mass of the battery decreases.
  • a tin compound such as a tin alloy (Cu—Sn alloy, Co—Sn alloy, etc.) can be exemplified.
  • polymer material examples include polyacetylene and polypyrrole.
  • the negative electrode active material a Si material obtained by heating a layered polysilane obtained by treating CaSi 2 with an acid such as hydrochloric acid or hydrofluoric acid at 300 to 1000 ° C. may be employed. Furthermore, the Si material heated with a carbon source and carbon coated may be adopted as the negative electrode active material.
  • the negative electrode active material one or more of the above can be used.
  • a current collecting method such as a roll coating method, a die coating method, a dip coating method, a doctor blade method, a spray coating method, or a curtain coating method
  • An active material may be applied to the surface of the body.
  • an active material, a solvent, and, if necessary, a binder and / or a conductive aid are mixed to prepare a slurry.
  • the solvent include N-methyl-2-pyrrolidone, methanol, methyl isobutyl ketone, and water.
  • the slurry is applied to the surface of the current collector and then dried. In order to increase the electrode density, the dried product may be compressed.
  • the electrolytic solution contains a non-aqueous solvent and an electrolyte dissolved in the non-aqueous solvent.
  • cyclic esters examples include ethylene carbonate, propylene carbonate, butylene carbonate, gamma butyrolactone, vinylene carbonate, 2-methyl-gamma butyrolactone, acetyl-gamma butyrolactone, and gamma valerolactone.
  • chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester, and acetic acid alkyl ester.
  • ethers examples include tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, and 1,2-dibutoxyethane.
  • non-aqueous solvent a compound in which part or all of hydrogen in the chemical structure of the specific solvent is substituted with fluorine may be employed.
  • Examples of the electrolyte include lithium salts such as LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 .
  • a lithium salt such as LiClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 in a nonaqueous solvent such as ethylene carbonate, dimethyl carbonate, propylene carbonate, and diethyl carbonate.
  • a solution dissolved at a concentration of about / L can be exemplified.
  • the separator separates the positive electrode and the negative electrode and allows lithium ions to pass while preventing a short circuit due to contact between the two electrodes.
  • natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, etc., polysaccharides such as cellulose, amylose, fibroin, keratin, lignin, suberin, etc. Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics.
  • the separator may have a multilayer structure.
  • a separator is sandwiched between the positive electrode and the negative electrode as necessary to form an electrode body.
  • the electrode body may be either a stacked type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are sandwiched.
  • an electrolyte is added to the electrode body and a lithium ion secondary Use batteries.
  • the lithium ion secondary battery of this invention should just be charged / discharged in the voltage range suitable for the kind of active material contained in an electrode.
  • the shape of the lithium ion secondary battery of the present invention is not particularly limited, and various shapes such as a cylindrical shape, a square shape, a coin shape, and a laminate shape can be adopted.
  • the lithium ion secondary battery of the present invention may be mounted on a vehicle.
  • the vehicle may be a vehicle that uses electric energy from a lithium ion secondary battery for all or a part of its power source, and may be, for example, an electric vehicle or a hybrid vehicle.
  • a lithium ion secondary battery is mounted on a vehicle, a plurality of lithium ion secondary batteries may be connected in series to form an assembled battery.
  • devices equipped with lithium ion secondary batteries include various home appliances driven by batteries such as personal computers and portable communication devices, office devices, and industrial devices in addition to vehicles.
  • the lithium ion secondary battery of the present invention includes wind power generation, solar power generation, hydroelectric power generation and other power system power storage devices and power smoothing devices, power supplies for ships and / or auxiliary power supply sources, aircraft, Power supply for spacecraft and / or auxiliary equipment, auxiliary power supply for vehicles that do not use electricity as a power source, power supply for mobile home robots, power supply for system backup, power supply for uninterruptible power supply, You may use for the electrical storage apparatus which stores temporarily the electric power required for charge in the charging station for electric vehicles.
  • Example 1 The material of Example 1 was manufactured as follows. a) Step LiNi 5/10 Co 3/10 Mn 2/10 O 2 having a layered rock salt structure was prepared as a lithium composite metal oxide. b) Step 100 g of the lithium composite metal oxide was added to 150 mL of pure water and stirred to obtain a dispersion. The pH of this dispersion was 11. Under stirring conditions, 3.8 g of B 2 O 3 was added to the above dispersion, and the temperature of the dispersion was increased to 40 ° C. to dissolve B 2 O 3 . Through the above operation, a dispersion liquid in which the lithium composite metal oxide was dispersed in the boron compound solution was prepared.
  • the lithium ion secondary battery of Example 1 was manufactured as follows. An aluminum foil having a thickness of 20 ⁇ m was prepared as a positive electrode current collector. 94 parts by mass of the material of Example 1 as an active material, 3 parts by mass of acetylene black as a conductive assistant, and 3 parts by mass of polyvinylidene fluoride (PVDF) as a binder were mixed. This mixture was dispersed in an appropriate amount of N-methyl-2-pyrrolidone (NMP) to prepare a slurry. The slurry was placed on the surface of the aluminum foil, and applied using a doctor blade so that the slurry became a film. The aluminum foil coated with the slurry was dried at 80 ° C.
  • NMP N-methyl-2-pyrrolidone
  • the aluminum foil having the active material layer formed on the surface thereof was compressed using a roll press, and the aluminum foil and the active material layer were firmly bonded.
  • the joined product was heated at 120 ° C. for 6 hours with a vacuum dryer, cut into a predetermined shape (rectangular shape of 25 mm ⁇ 30 mm), and used as a positive electrode.
  • the negative electrode was produced as follows. 98.3 parts by mass of graphite, 1 part by mass of styrene-butadiene rubber and 0.7 part by mass of carboxymethyl cellulose as a binder were mixed, and the mixture was dispersed in an appropriate amount of ion-exchanged water to prepare a slurry. This slurry was applied to a copper foil having a thickness of 20 ⁇ m as a negative electrode current collector so as to form a film using a doctor blade, and the current collector coated with the slurry was dried and pressed. It was heated with a vacuum dryer for a period of time and cut into a predetermined shape (rectangular shape of 25 mm ⁇ 30 mm) to obtain a negative electrode.
  • a laminate type lithium ion secondary battery was manufactured using the positive electrode and the negative electrode. Specifically, a rectangular sheet (27 ⁇ 32 mm, thickness 25 ⁇ m) made of a resin film having a three-layer structure of polypropylene / polyethylene / polypropylene was sandwiched between the positive electrode and the negative electrode to form an electrode plate group. The electrode plate group was covered with a set of two laminated films, and the three sides were sealed, and then an electrolyte solution was injected into the bag-like laminated film.
  • the electrolytic solution a solution obtained by dissolving LiPF 6 in a solvent obtained by mixing ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate in a volume ratio of 3: 3: 4 so as to be 1 mol / L was used. Thereafter, the remaining one side was sealed to obtain a laminate type lithium ion secondary battery of Example 1 in which the four sides were hermetically sealed and the electrode plate group and the electrolyte were sealed. Note that the positive electrode and the negative electrode have a tab that can be electrically connected to the outside, and a part of the tab extends to the outside of the laminated lithium ion secondary battery.
  • the lithium ion secondary battery of Example 1 was fabricated through the above steps.
  • Example 2 (Example 2) d) In the step, the material and lithium ion secondary battery of Example 2 were obtained in the same manner as in Example 1 except that 5 hours of preheating was added at 325 ° C. before heating at 475 ° C. It was.
  • Example 3 In the step d), the material of Example 3 was obtained in the same manner as in Example 1 except that it was heated at 400 ° C.
  • Example 4 In the step d), the material of Example 4 was obtained in the same manner as in Example 1 except that it was heated at 600 ° C.
  • Example 5 In the step d), the material of Example 5 was obtained in the same manner as in Example 1 except that it was heated at 750 ° C.
  • Comparative Example 1 In the step d), the material and the lithium ion secondary battery of Comparative Example 1 were prepared in the same manner as in Example 1 except that heating at 475 ° C. was not performed and heating was performed at 350 ° C. for 5 hours instead. Obtained.
  • Comparative Example 2 In the step d), the material of Comparative Example 2 was obtained in the same manner as in Comparative Example 1, except that heating was performed at 250 ° C.
  • Example 1 Example 1, Example 2, and Comparative Example 1 were subjected to composition analysis of Ni, Co, and Mn on the surface by X-ray photoelectron spectroscopy (XPS). The results are shown in Table 2.
  • Ni: Co: Mn of the lithium composite metal oxide was 5: 3: 2, it can be seen that the surface metal composition was changed by the heat treatment of each material.
  • the tip of the arrow shown in FIG. 2 is the edge portion of the primary particle, and the lower left direction from the edge portion is the internal direction of the primary particle.
  • the layer is mainly composed of B 2 O 3. (This layer is sometimes referred to as a B 2 O 3 layer.)
  • B 2 O 3 layer From the image of the layer of about 5 nm existing in the internal direction of the primary particle starting from the B 2 O 3 layer, an image of a transition metal showing a layered rock salt structure in the material of the present invention is observed. Compared with the internal image, it can be seen that the image is darker.
  • the material of the present invention has a boron-containing portion at a level of several nanometers.
  • the cross section of the primary particles in the material of Example 2 was analyzed by electron energy loss spectroscopy (EELS) for oxygen and boron. Then, a peak of non-oxygen oxygen bonded to the transition metal was observed from the edge part of the primary particle to the inside over about 2 nm, and a peak derived from oxygen bonded to the transition metal was observed in the internal direction of the portion. . Further, a boron peak derived from B 2 O 3 is observed from the edge portion of the primary particle to the inner direction about 7 nm, and further, a point from about 4 nm to the inner direction from the edge portion of the primary particle to a point of about 7 nm. Until now, the peak of boron derived from Co 2 B was observed. The result of analysis by EELS also confirmed the existence of the B 2 O 3 layer and the mixed layer of boron and transition metal.
  • EELS electron energy loss spectroscopy
  • the cross section of the primary particles in the material of Example 2 was analyzed for Ni, Co, and Mn with a transmission electron microscope-energy dispersive X-ray analyzer (TEM-EDX).
  • TEM-EDX transmission electron microscope-energy dispersive X-ray analyzer
  • the elemental ratio of Co was the highest, followed by Ni, and Mn was the lowest over about 15 nm from the edge portion of the primary particle to the inside.
  • the Ni element ratio was highest from the edge part of the primary particle to the inside, Co and Mn was the lowest. This result is consistent with the composition ratio of LiNi 5/10 Co 3/10 Mn 2/10 O 2 .
  • the surface transition metal composition is different from the internal transition metal composition. Specifically, in the material of the present invention, it can be said that the surface Co ratio is higher than the internal Co ratio and the surface Ni ratio is lower than the internal Ni ratio. It can be said that the transition metal composition on the surface of the material was reconstructed in the course of the production method of the present invention.
  • the initial capacities of the lithium ion secondary batteries of Examples 1 and 2 and Comparative Example 1 were measured as follows.
  • the battery to be measured is CCCV charged (constant current constant voltage charge) at 25 ° C., 0.33 C rate and voltage 4.5 V, and then CC discharge (constant current discharge) is performed at a rate of 0.33 C up to a voltage of 3.0 V.
  • the discharge capacity when measured was measured and used as the initial capacity.
  • the battery to be measured was subjected to 200 charge / discharge cycles in the range of voltage 4.5V to 3.0V at 60 ° C. and 1 C rate, and then left at room temperature for 5 hours or more, and under the same conditions as the initial capacity measurement.
  • the discharge capacity was measured. This was the post-cycle capacity.
  • the current rate at which the battery is completely discharged in 1 hour is referred to as 1C.
  • the secondary battery comprising the material of the present invention as an active material is excellent in initial capacity, post-cycle capacity, and capacity retention rate.
  • the lithium ion secondary battery of Example 1 after 200 cycles and the lithium ion secondary battery of Comparative Example 1 after 200 cycles were disassembled to determine how much Mn eluted from the positive electrode was attached to the negative electrode. Analysis was performed using an coupled plasma (ICP) emission spectrometer. As a result, the amount of Mn adhering to the negative electrode of the lithium ion secondary battery of Example 1 was 0.0065 mg, and the amount of Mn adhering to the negative electrode of the lithium ion secondary battery of Comparative Example 1 was 0.031 mg. Met. The amount of Mn adhering to the negative electrode of the lithium ion secondary battery of Example 1 was about 1/5 compared with that of Comparative Example 1. It was proved that the positive electrode comprising the material of the present invention as an active material can suppress Mn elution.
  • ICP coupled plasma
  • the secondary battery having the material of the present invention as an active material has low resistance.
  • the reason for the low resistance is presumed to be due to the presence of conductive MnB 2 and CoB formed on the surface of the material of the present invention.

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

Abstract

L'invention concerne un matériau d'un nouveau type qui est apte à être un matériau actif. Un procédé de production d'un matériau dans lequel une partie contenant du bore possédant une liaison B-Ni, une liaison B-Co ou une liaison B-Mn est formée sur la surface d'un oxyde métallique composite de lithium qui possède une structure feuilletée de sel gemme et est représenté par la formule générale LiaNibCocMndDeOf (dans laquelle 0,2 ≤ a ≤ 2 ; b + c + d + e = 1 ; 0 ≤ e < 1 ; D représente au moins un élément qui est choisi parmi Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf et Rf ; et 1,7 ≤ f ≤ 3). Ce procédé est caractérisé en ce qu'il comprend : (a) une étape de préparation de l'oxyde métallique composite de lithium ; (b) une étape de préparation d'un liquide de dispersion caractérisée en ce que l'oxyde métallique composite de lithium est dispersé dans une solution de composé de bore ; (c) une étape d'adhésion d'un composé de bore à la surface de l'oxyde métallique composite de lithium en diminuant la température de liquide du liquide de dispersion ; et (d) une étape de chauffage de l'oxyde métallique composite de lithium après l'étape (c) à une température de 400 °C ou plus.
PCT/JP2015/002712 2014-06-04 2015-05-28 Matériau possédant une partie d'oxyde métallique composite de lithium et une partie contenant du bore et son procédé de production WO2015186321A1 (fr)

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WO2019074305A3 (fr) * 2017-10-12 2019-06-06 주식회사 엘지화학 Matériau actif d'électrode positive pour batterie rechargeable au lithium, son procédé de préparation, électrode positive le comprenant pour batterie rechargeable au lithium et batterie rechargeable au lithium
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JP2020091985A (ja) * 2018-12-04 2020-06-11 株式会社豊田自動織機 二次電池
JP2021508161A (ja) * 2018-02-23 2021-02-25 エルジー・ケム・リミテッド 二次電池用正極活物質、その製造方法、及びこれを含むリチウム二次電池
KR20210112673A (ko) * 2020-03-05 2021-09-15 삼성에스디아이 주식회사 리튬이차전지용 복합양극활물질, 그 제조방법 및 이를 포함하는 양극을 함유한 리튬이차전지
CN113540466A (zh) * 2021-07-20 2021-10-22 浙江帕瓦新能源股份有限公司 一种金属硼化物与硼酸盐复合包覆改性的镍钴锰三元材料前驱体及其制备方法
CN114613988A (zh) * 2022-04-01 2022-06-10 湖南桑瑞新材料有限公司 一种高稳定性三元正极材料的制备方法、三元正极材料及锂离子电池
CN115084516A (zh) * 2021-07-28 2022-09-20 天津润光恒科技开发有限公司 一种硼基多元素复合材料的制备方法
WO2023054959A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지에너지솔루션 Procédé de fabrication d'un matériau actif de cathode pour batterie secondaire au lithium, et matériau actif de cathode ainsi fabirqué
EP4148826A4 (fr) * 2020-06-12 2024-09-18 Ecopro Bm Co Ltd Matériau actif de cathode et batterie rechargeable au lithium le comprenant

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JP2020024939A (ja) * 2015-12-21 2020-02-13 住友化学株式会社 正極活物質、リチウムイオン二次電池用正極およびリチウムイオン二次電池
JP2018045802A (ja) * 2016-09-13 2018-03-22 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とその製造方法、および該正極活物質を用いた非水系電解質二次電池
WO2018052038A1 (fr) * 2016-09-13 2018-03-22 住友金属鉱山株式会社 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, son procédé de production et batterie secondaire à électrolyte non aqueux utilisant ce matériau actif d'électrode positive
JP7051184B2 (ja) 2017-10-12 2022-04-11 エルジー・ケム・リミテッド リチウム二次電池用正極活物質、その製造方法、それを含むリチウム二次電池用正極及びリチウム二次電池
WO2019074305A3 (fr) * 2017-10-12 2019-06-06 주식회사 엘지화학 Matériau actif d'électrode positive pour batterie rechargeable au lithium, son procédé de préparation, électrode positive le comprenant pour batterie rechargeable au lithium et batterie rechargeable au lithium
CN110892565A (zh) * 2017-10-12 2020-03-17 株式会社Lg化学 锂二次电池用正极活性材料、其制备方法以及包含该正极活性材料的锂二次电池用正极和锂二次电池
JP2020525993A (ja) * 2017-10-12 2020-08-27 エルジー・ケム・リミテッド リチウム二次電池用正極活物質、その製造方法、それを含むリチウム二次電池用正極及びリチウム二次電池
CN110892565B (zh) * 2017-10-12 2022-07-01 株式会社Lg化学 正极活性材料、其制备方法以及包含其的锂二次电池用正极和锂二次电池
US11362332B2 (en) 2017-10-12 2022-06-14 Lg Chem, Ltd. Positive electrode active material for lithium secondary battery, method of preparing the same, and positive electrode for lithium secondary battery and lithium secondary battery which include the positive electrode active material
JP2021508161A (ja) * 2018-02-23 2021-02-25 エルジー・ケム・リミテッド 二次電池用正極活物質、その製造方法、及びこれを含むリチウム二次電池
JP7107196B2 (ja) 2018-12-04 2022-07-27 株式会社豊田自動織機 二次電池
JP2020091985A (ja) * 2018-12-04 2020-06-11 株式会社豊田自動織機 二次電池
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KR20210112673A (ko) * 2020-03-05 2021-09-15 삼성에스디아이 주식회사 리튬이차전지용 복합양극활물질, 그 제조방법 및 이를 포함하는 양극을 함유한 리튬이차전지
EP4148826A4 (fr) * 2020-06-12 2024-09-18 Ecopro Bm Co Ltd Matériau actif de cathode et batterie rechargeable au lithium le comprenant
CN113540466A (zh) * 2021-07-20 2021-10-22 浙江帕瓦新能源股份有限公司 一种金属硼化物与硼酸盐复合包覆改性的镍钴锰三元材料前驱体及其制备方法
CN115084516A (zh) * 2021-07-28 2022-09-20 天津润光恒科技开发有限公司 一种硼基多元素复合材料的制备方法
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WO2023054959A1 (fr) * 2021-10-01 2023-04-06 주식회사 엘지에너지솔루션 Procédé de fabrication d'un matériau actif de cathode pour batterie secondaire au lithium, et matériau actif de cathode ainsi fabirqué
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