WO2018025795A1 - Matière active d'électrode positive pour batteries secondaires à électrolyte non aqueux, électrode positive utilisant ladite matière active d'électrode positive et batterie secondaire - Google Patents

Matière active d'électrode positive pour batteries secondaires à électrolyte non aqueux, électrode positive utilisant ladite matière active d'électrode positive et batterie secondaire Download PDF

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WO2018025795A1
WO2018025795A1 PCT/JP2017/027642 JP2017027642W WO2018025795A1 WO 2018025795 A1 WO2018025795 A1 WO 2018025795A1 JP 2017027642 W JP2017027642 W JP 2017027642W WO 2018025795 A1 WO2018025795 A1 WO 2018025795A1
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positive electrode
active material
electrode active
secondary battery
electrolyte secondary
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PCT/JP2017/027642
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English (en)
Japanese (ja)
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基史 松田
肇 竹内
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株式会社三徳
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Priority to JP2018531878A priority Critical patent/JPWO2018025795A1/ja
Publication of WO2018025795A1 publication Critical patent/WO2018025795A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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 positive electrode active material, a positive electrode containing the positive electrode active material, and a non-aqueous electrolyte secondary battery using the positive electrode.
  • Lithium ion secondary batteries which are a type of non-aqueous electrolyte secondary battery, are widely used as batteries for portable electronic devices such as video cameras, portable audio players, mobile phones, and notebook computers. In recent years, it has become mainstream that such a lithium ion secondary battery is used under a high voltage of 4.30 V or more. When charged at a high voltage, more capacity can be used, but there is a problem that the amount of Li desorbed from the positive electrode active material increases and the positive electrode active material tends to deteriorate.
  • Patent Document 1 proposes a method of stabilizing the crystal structure by substituting part of Co in the positive electrode active material with Na or K.
  • Patent Document 2 Co, Al, and Mg are added to the positive electrode active material LiNiO 2 , and at least one of K, Na, Rb, or Cs is further added to efficiently suppress the collapse of the Li layer. A method has been proposed.
  • Patent Documents 1 and 2 have a problem that the structure is not sufficiently stabilized during high-voltage charging and the capacity is low. Under such circumstances, the present inventors substituted a part of Li in the lithium-containing composite oxide particles with Na, adhered a specific surface modifier on the particle surface, and set the content ratio of each element within a specific range. It was found that a positive electrode active material exhibiting excellent characteristics during high-voltage charging can be obtained by controlling to (see Patent Document 3).
  • Patent Document 3 It has been found that the positive electrode active material described in Patent Document 3 exhibits a high discharge capacity and capacity retention ratio (cycle characteristics) when charged at a high voltage of 4.50V. However, if a higher voltage of, for example, 4.55 V or higher is used, the capacity retention rate cannot be said to be sufficient, and further improvement is required.
  • an object of the present invention is to provide a positive electrode active material for a non-aqueous electrolyte secondary battery that can exhibit a sufficient discharge capacity and an excellent capacity retention rate when charged at a high voltage of 4.55 V or higher.
  • Another object of the present invention is to provide a positive electrode containing the positive electrode active material and a non-aqueous electrolyte secondary battery manufactured using the positive electrode.
  • the present inventors control the Li content ratio, the Na content ratio, the ratio of Li and Na to other elements, etc. within a specific range in a positive electrode active material composed of lithium-containing composite oxide particles and a surface modifying material. Thus, it has been found that excellent discharge characteristics can be achieved at the time of high voltage charging of 4.55 V or more, and the present invention has been completed.
  • the lithium-containing composite oxide particles and the surface modifying substance attached to the surface of the particles the following formula (1): Li xy Na y Co w Al a Mg b M c O 2+ ⁇ ⁇ (1)
  • x, y, w, a, b, c, and ⁇ are the formulas 0.986 ⁇ (xy) ⁇ 1.050, 0 ⁇ y ⁇ 0.020, 0.996 ⁇ x ⁇ 1.050, 0.990 ⁇ w ⁇ 1.015, 0.005 ⁇ a ⁇ 0.020, 0.001 ⁇ b ⁇ 0.020, 0.0005 ⁇ c ⁇ 0.005, and ⁇ 0.
  • the ratio (x) / (w + a + b + c) of (Li + Na) to (Co + Al + Mg + M) is 0.930 or more and less than 0.990, and M is Ca, rare earth element, Ti, Zr, Selected from Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, B, Ga, C, Si, Sn, N, P, S, F, Cl, and H One or more elements.
  • a positive electrode active material for a non-aqueous electrolyte secondary battery wherein the surface modifying material contains one or more elements selected from Al, Mg, and M.
  • a positive electrode containing the positive electrode active material and a nonaqueous electrolyte secondary battery including the positive electrode are provided.
  • the positive electrode active material of the present invention has the above-mentioned specific composition, it has high structural stability, and therefore can exhibit a sufficient discharge capacity and an excellent capacity retention rate (cycle characteristics) when charged at a high voltage of 4.55 V or higher. .
  • a nonaqueous electrolyte secondary battery using a positive electrode containing the positive electrode active material has excellent discharge characteristics during high-voltage charging.
  • the positive electrode active material of the present invention is a positive electrode active material for a nonaqueous electrolyte secondary battery having a composition represented by the following formula (1).
  • x, y, w, a, b, c, and ⁇ are represented by the formula 0.986 ⁇ (xy) ⁇ 1.050, 0 ⁇ y ⁇ 0.020, 0.996 ⁇ x.
  • the ratio (x) / (w + a + b + c) of (Li + Na) to (Co + Al + Mg + M) is 0.930 or more and less than 0.990, and M is Ca, rare earth element, Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, B, Ga, C, Si, Sn, N, P, S, F, Cl, and H One or more elements are shown.
  • x represents the total content ratio (molar ratio) of Li and Na.
  • x is a value within the range of 0.996 ⁇ x ⁇ 1.050. If x is less than 0.996, the stability in the Li desorption state may decrease. On the other hand, when x exceeds 1.050, the crystallinity is lowered, so that the charge / discharge capacity and the capacity retention ratio (cycle characteristics) are lowered.
  • the range of x is preferably 1.030 or less, more preferably 1.010 or less, and still more preferably 0.999 or less. When x is 0.999 or less, a very excellent capacity maintenance ratio can be obtained particularly when charging at a high voltage of 4.55 V or more.
  • (xy) represents the content ratio (molar ratio) of Li.
  • (Xy) is a value in the range of 0.986 ⁇ (xy) ⁇ 1.050.
  • (xy) is less than 0.986, the stability of the crystal structure in the Li desorption state may be reduced.
  • (xy) is 1.050 or more, the crystallinity is lowered, so that the charge / discharge capacity and the capacity retention rate are lowered.
  • the range of (xy) is preferably less than 1.030, more preferably 1.003 or less, and still more preferably 0.990 or less. When (xy) is 0.990 or less, a very excellent capacity retention rate can be obtained particularly when charging at a high voltage of 4.55 V or more.
  • y represents the content ratio (molar ratio) of Na.
  • Na is dissolved in the layer of LiCoO 2 that is a layered compound, and can suppress the collapse of the crystal structure during charging when Li is desorbed. This is presumed to be because Na has a lower mobility than Li and takes time to pull out by applying a voltage, so it stays between the layers, suppresses the collapse of the crystal structure, and improves the durability during charging. Is done.
  • y it is possible to suppress the collapse of the crystal structure due to the detachment of Li, especially during continuous charging or high voltage charging of 4.3 V or higher. can get. Since Na has a larger ionic radius than Li, if a part of Li is replaced with Na, the interlayer expands.
  • y is 0 ⁇ y ⁇ 0.020.
  • y is preferably 0.002 or more, more preferably 0.004 or more.
  • y is preferably 0.018 or less, more preferably 0.010 or less. If y exceeds 0.020, it is presumed that the battery characteristics will be adversely affected, for example, Na will be excessive and Na will not enter the Li layer and the crystal structure cannot be maintained.
  • w represents the content ratio (molar ratio) of Co.
  • Co is one of the main elements constituting the positive electrode active material of the present invention.
  • the range of w is 0.990 ⁇ w ⁇ 1.015.
  • w is less than 0.990, the discharge capacity and the capacity retention rate decrease.
  • w exceeds 1.015, the stability of the crystal structure decreases.
  • a represents the Al content ratio (molar ratio). Al stabilizes the crystal structure, thereby improving thermal stability and continuous charge characteristics.
  • the range of a is 0.005 ⁇ a ⁇ 0.020, and preferably 0.010 ⁇ a ⁇ 0.016. When a is less than 0.005, the continuous charge characteristics are deteriorated. On the other hand, when a exceeds 0.020, the discharge capacity decreases.
  • b represents the content ratio (molar ratio) of Mg.
  • Mg stabilizes the crystal structure, thereby improving thermal stability and continuous charge characteristics.
  • the range of b is 0.001 ⁇ b ⁇ 0.020, and preferably 0.005 ⁇ b ⁇ 0.012. If b is less than 0.001, the structure stabilizing effect may not be sufficiently exhibited. On the other hand, if b exceeds 0.020, the specific surface area may become too small.
  • c represents the content ratio (molar ratio) of M.
  • M is Ca, rare earth element, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, B, Ga, C, Si, Sn, N, P 1 or more elements selected from S, F, Cl, and H. That is, M represents an element other than Li, Na, Co, Al, Mg, and O contained in the positive electrode active material of the present invention.
  • c represents the total content ratio (molar ratio) of the plurality of elements.
  • the range of c is 0.0005 ⁇ c ⁇ 0.005, and preferably 0.001 ⁇ c ⁇ 0.003.
  • “rare earth element” includes Y, Sc, and lanthanoid.
  • the stability of the crystal structure is further improved.
  • the content ratio (molar ratio) of Zr is preferably 0.0001 or more and less than 0.005, and more preferably 0.0005 or more and 0.003 or less. If the Zr content is less than 0.0001, the effect of improving the stability may not be sufficiently exhibited, and if it is 0.005 or more, the specific surface area may be too small.
  • the Li deintercalation or intercalation speed at the time of charge / discharge is increased, so that the load characteristics are improved.
  • the content ratio (molar ratio) of Ti is preferably 0.0001 or more and less than 0.005, and more preferably 0.0005 or more and 0.003 or less. If the Ti content is less than 0.0001, the load characteristic improvement effect may not be sufficiently exhibited, and if it is 0.005 or more, the growth of primary particles is suppressed, and the number of primary particles forming secondary particles is small. May increase.
  • the positive electrode active material of the present invention preferably contains both Ti and Zr as M. In this case, it is possible to manufacture a battery exhibiting high load characteristics and high capacity with stable quality using the positive electrode active material.
  • (2 + ⁇ ) represents the oxygen content (molar ratio).
  • the range of ⁇ is ⁇ 0.1 ⁇ ⁇ ⁇ 0.1, and is determined by the content ratio of Li, Na, Co, Al, Mg, and M.
  • (X) / (w + a + b + c) represents the molar ratio of (Li + Na) to (Co + Al + Mg + M).
  • the molar ratio (x) / (w + a + b + c) is 0.930 or more, preferably 0.960 or more, more preferably 0.965 or more.
  • the molar ratio (x) / (w + a + b + c) is less than 0.990, preferably 0.980 or less, and more preferably 0.975 or less. When this molar ratio is less than 0.930, the structural stability during charging is extremely lowered. On the other hand, when it is 0.990 or more, the capacity maintenance rate at the time of high voltage charging of 4.55 V or more may decrease. When this molar ratio is 0.980 or less, the discharge capacity is particularly improved.
  • the positive electrode active material of the present invention comprises lithium-containing composite oxide particles and a surface modifying material attached to the surface of the composite oxide particles. That is, the above formula (1) represents the total composition of the composite oxide particles and the surface modifier. This composition can be measured by quantitative analysis with an ICP (Inductively Coupled Plasma) analyzer.
  • ICP Inductively Coupled Plasma
  • the composite oxide particles include Li, Na, Co, and O, and optionally, Al, Mg, Ca, rare earth elements, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, One or more elements selected from Ni, Cu, Ag, Zn, B, Ga, C, Si, Sn, N, P, S, F, Cl, and H may be included.
  • the composite oxide particles are preferably composed of Li, Na, Co, and O, and one or more elements selected from Mg, Ti, and Zr.
  • the surface modifier contains one or more elements selected from Al, Mg, and M.
  • Surface modifying substances are Al, Mg, Ca, rare earth elements, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, B, Ga, Si, and It is preferable to include one or more elements selected from Sn, and optionally to include one or more elements selected from Li, Na, Co, O, C, N, P, S, F, Cl, and H. You may go out. More preferably, the surface modifying material contains one or more elements selected from Al, Mg, Ti, Zr, and La. From the viewpoint of improving the capacity retention rate, it is particularly preferable that the surface modifier contains Al.
  • the surface modifying substance may be an inorganic compound such as a hydroxide, an oxide, or a carbonate, or may be a substance derived from the inorganic compound.
  • the inorganic compound include aluminum nitrate, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, and an oxide having lithium ion conductivity.
  • the surface modifying substance is uniformly dispersed on the surface of the composite oxide particle.
  • “the surface modifying substance is attached to the surface of the composite oxide particle” means that the surface modifying substance is held in contact with the surface. It may be in a state of being adsorbed or adhered to the surface, or in a state in which the surface modifying substance is chemically bonded to the surface.
  • the method for preparing the composite oxide particles is not particularly limited.
  • a lithium compound as a lithium source, a sodium compound as a sodium source, a cobalt compound as a cobalt source, an aluminum compound as an aluminum source, a magnesium compound as a magnesium source, and an M-containing compound as an M source are obtained.
  • the resulting mixture can be fired to prepare composite oxide particles.
  • lithium compound examples include inorganic salts such as lithium hydroxide, lithium chloride, lithium nitrate, lithium carbonate, and lithium sulfate, and organic salts such as lithium formate, lithium acetate, and lithium oxalate.
  • inorganic salts such as lithium hydroxide, lithium chloride, lithium nitrate, lithium carbonate, and lithium sulfate
  • organic salts such as lithium formate, lithium acetate, and lithium oxalate.
  • Examples of the sodium compound include inorganic salts such as sodium hydroxide, sodium chloride, sodium nitrate, sodium carbonate, and sodium sulfate, and organic salts such as sodium formate, sodium acetate, and sodium oxalate.
  • inorganic salts such as sodium hydroxide, sodium chloride, sodium nitrate, sodium carbonate, and sodium sulfate
  • organic salts such as sodium formate, sodium acetate, and sodium oxalate.
  • cobalt compound examples include oxides, hydroxides, carbonates, oxyhydroxides, and the like. Cobalt oxide is preferably used.
  • the shape of the positive electrode active material is affected by the shape of the cobalt compound. Therefore, the shape of the positive electrode active material can be controlled by making the cobalt compound spherical or elliptical and adjusting the particle size, particle size distribution, and the like.
  • Examples of the aluminum compound include aluminum hydroxide, aluminum chloride, aluminum oxide, aluminum carbonate, aluminum nitrate, aluminum sulfate, and aluminum formate.
  • magnesium compound examples include magnesium hydroxide, magnesium carbonate, magnesium chloride, magnesium peroxide, magnesium oxide, magnesium nitrate, magnesium acetate, magnesium sulfate and the like.
  • M-containing compound examples include M-containing oxides, hydroxides, carbonates, sulfates, nitrates, halides, and the like. Depending on the element selected, the M-containing compound may be a gas containing M.
  • a predetermined amount of each of a lithium compound, a sodium compound, a cobalt compound, an aluminum compound, a magnesium compound, and an M-containing compound is weighed and mixed.
  • Mixing can be performed by a known method using a ball mill or the like, but it is preferable to use a high-speed stirring mixer to improve dispersibility.
  • the obtained mixture is fired. Firing can be performed by a known method using a cart furnace, a kiln furnace, a mesh belt furnace, or the like.
  • the calcination temperature may be 950 to 1050 ° C., preferably 1030 to 1050 ° C.
  • the firing time may be 1 to 24 hours.
  • the main baking may be performed by raising the temperature to the baking temperature.
  • Pre-baking and annealing are preferably performed at 500 to 800 ° C. for about 30 minutes to 6 hours.
  • lithium source sodium source
  • cobalt source aluminum source
  • magnesium source magnesium source
  • M source magnesium source
  • composite compounds may also be used.
  • a method in which Co, Al, Mg, and M are combined by a coprecipitation method to prepare a composite compound, which is mixed with a lithium compound and a sodium compound, and the resulting mixture is fired is also preferably performed.
  • the surface-modifying substance can be attached to the composite oxide particles by mixing the composite oxide particles with the raw material of the surface-modifying substance in a solvent and filtering and baking the resulting mixture. What is necessary is just to adjust the quantity of the composite oxide particle to mix and the amount of surface modification substance raw material so that the composition of Formula (1) may be obtained.
  • the molar ratio of the surface modifying material raw material to the composite oxide is 0.05 to 0.50 mol%. Of course, this molar ratio is the ratio of the composite oxide particles and the surface modifying material in the mixing step, and not the ratio of the composite oxide particles and the surface modifying material in the positive electrode active material.
  • the firing step may be performed at 200 to 700 ° C. for about 1 to 10 hours.
  • a method including the following steps is exemplified as a method of attaching the surface modifying substance to the composite oxide particles.
  • Step 1 Each of the composite oxide particles, the raw material of the surface modifying substance, and lithium hydroxide monohydrate (pH adjuster) is weighed.
  • Step 2 Lithium hydroxide monohydrate is dissolved in 100 mL of pure water, and then mixed oxide particles are added to prepare a first slurry liquid.
  • Step 3) A surface modifying substance raw material solution is prepared by dissolving a surface modifying substance raw material in 10 mL of pure water.
  • Step 4) The surface modifying substance raw material liquid is charged into the first slurry liquid to prepare a second slurry liquid.
  • Step 5 Stir the second slurry to stabilize the pH.
  • Step 6 The second slurry liquid whose pH is stabilized is filtered, and the obtained cake (filtrate) is washed with pure water.
  • Step 7) By baking the washed cake, the surface modifying substance is attached to the surface of the composite oxide particles, and a positive electrode active material is obtained.
  • Cleaning may be performed during the manufacturing process of the positive electrode active material.
  • Na that could not be completely dissolved between the layers of the composite oxide can be removed, thereby reducing Na eluted in the electrolytic solution and inhibiting insertion / extraction of lithium ions generated in the electrolytic solution.
  • Side reactions can be suppressed, and deterioration of charge / discharge characteristics due to Na can be minimized.
  • this washing may be performed before or after the surface modifier is attached to the surface of the composite oxide particle as long as the side reaction can be suppressed.
  • the aluminum nitrate when used as a raw material for the surface modifying substance, at least a part of the aluminum nitrate can be converted into aluminum hydroxide in the mixing step.
  • aluminum oxide or metal aluminum (aluminum alone) may be generated from aluminum hydroxide, and at least a part of the aluminum hydroxide may remain as it is. That is, in this case, by appropriately selecting the conditions of each step, aluminum nitrate, aluminum hydroxide, aluminum oxide, and / or aluminum simple substance can be attached to the surface of the composite oxide particle as a surface modifier.
  • one or more substances may be attached to the composite oxide particles as the surface modifying substance.
  • the above formula (1) represents the total composition of the plurality of substances and the composite oxide particles.
  • each element of the formula (1) is not uniformly distributed over the entire positive electrode active material, and the surface of the positive electrode active material is a surface modifying material.
  • the content ratio of the contained elements increases.
  • the positive electrode active material has a special composition and structure, and thus exhibits a remarkable effect.
  • the average particle diameter of the positive electrode active material is not particularly limited, but is preferably about 2 to 50 ⁇ m so that a sufficient density can be obtained when it is applied to the electrode plate. In order to improve the density, a plurality of positive electrode active materials having different average particle diameters within the average particle diameter range may be mixed.
  • the positive electrode for a non-aqueous electrolyte secondary battery of the present invention contains the above-described positive electrode active material of the present invention.
  • the positive electrode active material exhibits a stable crystal structure during charging, so that there is little deterioration due to continuous charging or high voltage charging, and high capacity and high capacity retention are achieved.
  • the positive electrode of the present invention may be produced by a known method. For example, a positive electrode active material and a conductive agent or a binder are kneaded in a dispersion medium, and the resulting slurry is applied to an electrode plate, dried, roller-rolled, cut into a predetermined size, and the positive electrode is Can be made.
  • the positive electrode active material of the present invention is used, the positive electrode active material, the conductive agent, the binder, and the like are uniformly dispersed, the slurry exhibits appropriate fluidity, and changes with time are small.
  • the thickness of the positive electrode is 40 to 120 ⁇ m.
  • the conductive agent binder, dispersion medium, electrode plate, etc. for producing the positive electrode
  • known ones can be used.
  • the conductive agent include carbonaceous materials such as natural graphite, artificial graphite, ketjen black, and acetylene black.
  • binders fluorine resins (polytetrafluoroethylene, polyvinylidene fluoride, etc.), polyvinyl acetate, polymethyl methacrylate, ethylene-propylene-butadiene copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer Examples thereof include merging and carboxymethylcellulose.
  • dispersion medium examples include N-methylpyrrolidone, tetrahydrofuran, ethylene oxide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, dimethylformamide, dimethylacetamide and the like.
  • a porous or non-porous conductive substrate is used as the electrode plate.
  • the conductive substrate include metal foils such as Al, Cu, Ti, and stainless steel. Of these, an Al foil is preferable, and the thickness of the Al foil is preferably 10 to 30 ⁇ m.
  • the nonaqueous electrolyte secondary battery of the present invention has the above-described positive electrode for a nonaqueous electrolyte secondary battery of the present invention.
  • the positive electrode active material exhibits a stable crystal structure during charging, so that there is little deterioration due to continuous charging or high voltage charging, and a high capacity and a high capacity retention rate are achieved.
  • the nonaqueous electrolyte secondary battery of the present invention is mainly composed of a battery case, a positive electrode, a negative electrode, an organic solvent, an electrolyte, and a separator.
  • a solid electrolyte may be used instead of the organic solvent and the electrolyte (electrolyte solution).
  • Known materials can be used as the negative electrode, organic solvent, electrolyte, and separator.
  • the negative electrode is obtained by applying a negative electrode mixture in which a negative electrode active material, a binder, a conductive agent, a dispersion medium, and the like are mixed on a current collector made of a metal foil such as Cu, and then rolling and drying. It is done.
  • a negative electrode active material lithium metal, lithium alloy, amorphous carbon artificial graphite (soft carbon, hard carbon, etc.), carbonaceous material (natural graphite, etc.) and the like are used. If necessary, the same binder and dispersion medium as those for the positive electrode are used.
  • the type of the organic solvent is not particularly limited.
  • carbonates propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, etc.
  • ethers (1,2-dimethoxypropane, 1,3-dimethoxypropane, Tetrahydrofuran, 2-methyltetrahydrofuran, etc.
  • esters methyl acetate, ⁇ -butyrolactone, etc.
  • nitriles acetonitrile, butyronitrile, etc.
  • amides N, N-dimethylformamide, N, N-dimethylacetamide, etc.
  • Examples of the electrolyte dissolved in the organic solvent include LiClO 4 , LiPF 6 , LiBF 4 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , Li (CF 3 SO 2 ) 2 , LiAsF 6 ,
  • Examples include LiB 10 Cl 10 , lower aliphatic lithium carboxylate, lithium tetrachloroborate, lithium tetraphenylborate, and imides. These may be used alone or in combination of two or more.
  • solid electrolytes examples include polymer electrolytes (polyethylene oxide electrolytes, etc.), sulfide electrolytes (Li 2 S—SiS 2 , Li 2 SP—S 2 S 5 , Li 2 S—B 2 S 3 etc.), etc. Is mentioned.
  • a so-called gel type electrolyte in which a nonaqueous electrolyte solution is held in a polymer can also be used.
  • a microporous thin film having high ion permeability, predetermined mechanical strength, and electronic insulation is preferably used.
  • a microporous thin film made of a material such as polyethylene, polypropylene, polyphenylene sulfide, polyethylene terephthalate, polyamide, or polyimide because of its excellent resistance to electrolyte and hydrophobicity. These materials may be used alone or in combination. From the viewpoint of manufacturing cost, it is preferable to use inexpensive polypropylene or the like.
  • the shape of the nonaqueous electrolyte secondary battery of the present invention can be selected from various shapes such as a cylindrical shape, a laminated shape, and a coin shape. Regardless of the shape, the above-described components are housed in the battery case, and the space between the positive electrode and the negative electrode to the positive electrode terminal and the negative electrode terminal is connected with a current collecting lead or the like, and the battery case is sealed.
  • Example 1 Manufacture of positive electrode active material
  • Lithium carbonate, sodium carbonate, cobalt oxide, aluminum hydroxide, magnesium hydroxide, titanium oxide, and zirconium oxide were weighed so that the positive electrode active material finally obtained had the composition shown in Table 1, and a high-speed stirring mixer To obtain a mixture.
  • the mixture was calcined at 700 ° C. for 4 hours using a box-type electric furnace, and then baked at 1030 ° C. for 5 hours to obtain a composite oxide.
  • Lithium hydroxide monohydrate was dissolved in 100 mL of pure water, and a composite oxide was added thereto to prepare a first slurry liquid.
  • aluminum nitrate nonahydrate was dissolved in 10 mL of pure water to prepare a surface modifying material raw material liquid.
  • the surface modifier material liquid is put into the first slurry liquid at a rate of 5 mL / min using a pipetter, it is stirred for 5 minutes or more, and it is confirmed that the pH is stable at around 10.7, and then the second slurry. A liquid was obtained.
  • the second slurry was filtered, and the resulting cake was washed with 200 mL of pure water.
  • the washed cake was heated to 500 ° C. at a temperature rising rate of 5 ° C./min, and baked for 3 hours after reaching 500 ° C. to obtain a positive electrode active material having the composition shown in Table 1.
  • This positive electrode active material is composed of composite oxide particles and an Al-containing surface modifier adhering to the surface.
  • the obtained positive electrode active material, graphite and acetylene black (conductive agent), and polyvinylidene fluoride (binder) were mixed at a mass ratio of 200: 4: 1: 10 and kneaded in N-methylpyrrolidone.
  • An electrode slurry was obtained. This electrode slurry was applied to an aluminum foil having a thickness of 20 ⁇ m, dried, press-molded to a thickness of 40 ⁇ m with a press machine, cut into a predetermined size, and terminals were spot welded to produce a positive electrode.
  • a test coin cell secondary battery was produced as follows. Metal lithium foil was used as a counter electrode (negative electrode), the positive electrode was used as a test electrode, and these were arranged in a battery case via a separator. A coin cell secondary battery was manufactured by injecting an electrolytic solution therein. The electrolytic solution was prepared by dissolving LiPF 6 as a supporting electrolyte at a concentration of 1M in a 1: 2 (volume ratio) mixed solvent of ethylene carbonate (EC) and dimethyl carbonate (DMC).
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • a charge / discharge test was performed as follows using the manufactured coin cell secondary battery. (1) The measurement temperature was 25 ° C., and in the first and second cycles, charging and discharging were performed under the conditions of a charge upper limit voltage 4.55 V, a discharge lower limit voltage 3.0 V, and a current density of 0.3 mA / cm 2 . (2) From the third cycle onward, charging / discharging was performed under the conditions of a charge upper limit voltage of 4.55 V, a discharge lower limit voltage of 3.0 V, and a current density of 1.5 mA / cm 2 .
  • Capacity retention rate (%) (discharge capacity at 22nd cycle / discharge capacity at 3rd cycle) ⁇ 100 Table 1 shows the discharge capacity and capacity retention rate of the first cycle.
  • Examples 2 to 6 and Comparative Examples 1 to 18 Cathode active materials of Examples 2 to 6 and Comparative Examples 1 to 18 were produced in the same manner as in Example 1 except that the composition of the raw material compounds was changed and the compositions shown in Table 1 were finally obtained. In addition, manganese sulfate (II) pentahydrate was used as a manganese source. A coin cell secondary battery was produced using each positive electrode active material in the same manner as in Example 1, and a charge / discharge test was performed. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

L'invention concerne : une matière active d'électrode positive qui est capable de présenter une capacité de décharge suffisante et un excellent taux de rétention de capacité pendant une charge à haute tension ; une électrode positive qui utilise cette matière active d'électrode positive ; et une batterie secondaire. Cette matière active d'électrode positive est composée de particules d'oxyde composite contenant du lithium et d'un matériau de modification de surface collé aux surfaces des particules, et a une composition représentée par la formule (1). Le matériau de modification de surface contient un ou plusieurs éléments choisis parmi Al, Mg et M. Lix-yNayCowAlaMgbMcO2+α (1) (Dans la formule (1), x, y, w, a, b, c et α satisfont les formules 0,986 ≤ (x - y) < 1,050, 0 < y ≤ 0,020, 0,996 ≤ x ≤ 1,050, 0,990 ≤ w ≤ 1,015, 0,005 ≤ a ≤ 0,020, 0,001 ≤ b ≤ 0,020, 0,0005 ≤ c ≤ 0,005 et -0,1 ≤ α ≤ 0,1 ; le rapport de (Li + Na) à (Co + Al + Mg + M), à savoir (x)/(w + a + b + c) est supérieur ou égal à 0,930 mais inférieur à 0,990 ; et M représente un ou plusieurs éléments choisis parmi Ca, des éléments de terres rares, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ni, Cu, Ag, Zn, B, Ga, C, Si, Sn, N, P, S, F, Cl et H.)
PCT/JP2017/027642 2016-08-04 2017-07-31 Matière active d'électrode positive pour batteries secondaires à électrolyte non aqueux, électrode positive utilisant ladite matière active d'électrode positive et batterie secondaire WO2018025795A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102126898B1 (ko) * 2019-12-05 2020-06-25 주식회사 에스엠랩 양극활물질, 이의 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
JP2020198194A (ja) * 2019-05-31 2020-12-10 住友金属鉱山株式会社 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池
WO2021095360A1 (fr) * 2019-11-14 2021-05-20 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
CN113424340A (zh) * 2019-02-28 2021-09-21 Sm研究所股份有限公司 阳极活性物质、其制备方法以及包括该阳极活性物质的阳极的锂二次电池
KR20210133803A (ko) * 2020-04-29 2021-11-08 주식회사 에스엠랩 리튬 이차전지용 양극활물질, 그의 제조방법 및 이를 포함하는 리튬이차전지
CN115000397A (zh) * 2022-04-19 2022-09-02 中国第一汽车股份有限公司 一种固态电池正极材料及其制备方法和固态电池正极
CN117239111A (zh) * 2023-11-13 2023-12-15 北京中科海钠科技有限责任公司 无镍层状氧化物正极材料、其制备方法、正极组合物、钠离子二次电池和用途
WO2024046011A1 (fr) * 2022-08-30 2024-03-07 珠海冠宇电池股份有限公司 Matériau d'électrode positive, procédé de préparation de matériau d'électrode positive, feuille d'électrode positive et batterie
WO2024055749A1 (fr) * 2022-09-13 2024-03-21 珠海冠宇电池股份有限公司 Matériau d'électrode positive, et feuille d'électrode positive et batterie les comprenant
WO2024153145A1 (fr) * 2023-01-17 2024-07-25 珠海冠宇电池股份有限公司 Matériau d'électrode positive et batterie le comprenant

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011170994A (ja) * 2010-02-16 2011-09-01 Sanyo Electric Co Ltd 非水電解質二次電池及びその製造方法
WO2012039413A1 (fr) * 2010-09-22 2012-03-29 株式会社Ｇｓユアサ Substance active et électrode pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2015005439A1 (fr) * 2013-07-11 2015-01-15 株式会社三徳 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et électrode positive et batterie secondaire utilisant ledit matériau actif d'électrode positive
JP2015118762A (ja) * 2013-12-17 2015-06-25 旭硝子株式会社 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
JP2015144108A (ja) * 2013-12-27 2015-08-06 旭硝子株式会社 リチウムイオン二次電池正極用の表面修飾リチウム含有複合酸化物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011170994A (ja) * 2010-02-16 2011-09-01 Sanyo Electric Co Ltd 非水電解質二次電池及びその製造方法
WO2012039413A1 (fr) * 2010-09-22 2012-03-29 株式会社Ｇｓユアサ Substance active et électrode pour batterie secondaire au lithium, et batterie secondaire au lithium
WO2015005439A1 (fr) * 2013-07-11 2015-01-15 株式会社三徳 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et électrode positive et batterie secondaire utilisant ledit matériau actif d'électrode positive
JP2015118762A (ja) * 2013-12-17 2015-06-25 旭硝子株式会社 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
JP2015144108A (ja) * 2013-12-27 2015-08-06 旭硝子株式会社 リチウムイオン二次電池正極用の表面修飾リチウム含有複合酸化物

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113424340A (zh) * 2019-02-28 2021-09-21 Sm研究所股份有限公司 阳极活性物质、其制备方法以及包括该阳极活性物质的阳极的锂二次电池
CN113424340B (zh) * 2019-02-28 2024-05-17 Sm研究所股份有限公司 阳极活性物质、其制备方法以及包括该阳极活性物质的阳极的锂二次电池
JP2020198194A (ja) * 2019-05-31 2020-12-10 住友金属鉱山株式会社 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池
JP7274125B2 (ja) 2019-05-31 2023-05-16 住友金属鉱山株式会社 全固体リチウムイオン二次電池用正極活物質および全固体リチウムイオン二次電池
WO2021095360A1 (fr) * 2019-11-14 2021-05-20 パナソニックＩｐマネジメント株式会社 Matériau actif d'électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
CN114762149A (zh) * 2019-12-05 2022-07-15 Sm研究所股份有限公司 正极活性材料、所述正极活性材料的制备方法以及具有包括所述正极活性材料的正极的锂二次电池
KR102350597B1 (ko) * 2019-12-05 2022-01-18 주식회사 에스엠랩 양극활물질, 이의 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
CN114762149B (zh) * 2019-12-05 2024-04-05 Sm研究所股份有限公司 正极活性材料、所述正极活性材料的制备方法以及具有包括所述正极活性材料的正极的锂二次电池
KR102126898B1 (ko) * 2019-12-05 2020-06-25 주식회사 에스엠랩 양극활물질, 이의 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
JP2023505185A (ja) * 2019-12-05 2023-02-08 エスエム ラブ コーポレーション リミテッド 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
KR20210070893A (ko) * 2019-12-05 2021-06-15 주식회사 에스엠랩 양극활물질, 이의 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
WO2021112323A1 (fr) * 2019-12-05 2021-06-10 주식회사 에스엠랩 Matériau actif positif, son procédé de préparation, et batterie rechargeable au lithium à électrode positive le comprenant
JP7402566B2 (ja) 2019-12-05 2023-12-21 エスエム ラブ コーポレーション リミテッド 正極活物質、その製造方法、及びそれを含む正極を含むリチウム二次電池
KR20210133803A (ko) * 2020-04-29 2021-11-08 주식회사 에스엠랩 리튬 이차전지용 양극활물질, 그의 제조방법 및 이를 포함하는 리튬이차전지
KR102386904B1 (ko) * 2020-04-29 2022-04-15 주식회사 에스엠랩 리튬 이차전지용 양극활물질, 그의 제조방법 및 이를 포함하는 리튬이차전지
CN115000397A (zh) * 2022-04-19 2022-09-02 中国第一汽车股份有限公司 一种固态电池正极材料及其制备方法和固态电池正极
WO2024046011A1 (fr) * 2022-08-30 2024-03-07 珠海冠宇电池股份有限公司 Matériau d'électrode positive, procédé de préparation de matériau d'électrode positive, feuille d'électrode positive et batterie
WO2024055749A1 (fr) * 2022-09-13 2024-03-21 珠海冠宇电池股份有限公司 Matériau d'électrode positive, et feuille d'électrode positive et batterie les comprenant
WO2024153145A1 (fr) * 2023-01-17 2024-07-25 珠海冠宇电池股份有限公司 Matériau d'électrode positive et batterie le comprenant
CN117239111B (zh) * 2023-11-13 2024-02-02 北京中科海钠科技有限责任公司 无镍层状氧化物正极材料、其制备方法、正极组合物、钠离子二次电池和用途
CN117239111A (zh) * 2023-11-13 2023-12-15 北京中科海钠科技有限责任公司 无镍层状氧化物正极材料、其制备方法、正极组合物、钠离子二次电池和用途

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