Cathode active materials for solid-state rechargeable batteries

Abstract

The present invention relates to a cathode active material for a solid state rechargeable battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, characterized in that it further comprises fluorine, the atomic ratio of F to the total amount of Ni, Mn, and / or Co being ≧0.05 and ≦3.0 as determined by XPS analysis, and carbon, the carbon content being ≧370 ppm and ≦5000 ppm as determined by a carbon analyzer, based on the total weight of the cathode active material.

Description

[Technical Field]

[0001] The present invention relates to a cathode active material for a solid-state rechargeable battery. More specifically, the present invention relates to a cathode active material containing an F atom for a solid-state battery, preferably a polymer-based solid-state battery. The present invention also relates to a method for producing the cathode active material. Furthermore, the present invention relates to a solid-state battery containing the cathode active material. [Background technology]

[0002] The present invention relates to the use of a single-crystalline positive electrode active material powder containing F for solid-state rechargeable batteries.

[0003] Such a cathode active material containing elemental aluminum and fluorine on the surface layer is already known, for example, from WO 2016 / 116862 (Al). This document discloses a cathode active material containing F, in which F is introduced into the cathode active material by mixing a lithium transition metal oxide with polyvinylidene fluoride (PVDF) and then heating at 375°C. The cathode active material prepared according to this method showed low retention when applied to an electrochemical cell. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2016 / 116862 Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, an object of the present invention is to provide a positive electrode active material having good electrochemical properties.

[0006] A further object of the present invention is to provide a method for producing the positive electrode active material.

[0007] A further object of the present invention is to provide a positive electrode active material obtained by the method.

[0008] A further object of the present invention is to provide a solid-state battery containing the positive electrode active material.

[0009] A further object of the present invention is to provide the use of the cathode active material in a solid-state battery.

[0010] A further object of the present invention is to provide a use of the solid-state battery. [Means for solving the problem]

[0011] The object is achieved by providing a cathode active material for a solid-state battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, characterized in that the cathode active material further comprises fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or more and 3.0 or less, as determined by XPS analysis, and carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, based on the total weight of the cathode active material, as determined by a carbon analyzer.

[0012] As shown by the examples and supported by the results shown in Table 2, a lower total leakage capacity (Q total ) and high retention is indeed observed.

[0013] A further aspect of the present invention is a method for producing a cathode active material, the method comprising the steps of: mixing a lithium transition metal oxide compound with an F-containing polymer; and heating the mixture at a temperature of less than 350°C in an oxidizing atmosphere in a furnace for a time period of 1 hour to 20 hours to obtain the cathode active material.

[0014] A further aspect of the present invention is a positive electrode active material obtainable by the method.

[0015] A further aspect of the present invention is a solid-state rechargeable battery that includes the positive electrode active material. DETAILED DESCRIPTION OF THE INVENTION

[0016] Unless otherwise defined, all terms used in disclosing the present invention, including technical and scientific terms, have the meanings commonly understood by one of ordinary skill in the art to which this invention belongs. By way of further guidance, definitions of terms are included to better understand the teachings of the present invention. As used herein, the following terms have the following meanings: The term "ppm," as used herein, means parts per million by mass.

[0017] As used herein, "about" referring to a measurable value such as a parameter, amount, duration, etc., is meant to encompass a variation of no more than ±20%, preferably no more than ±10%, more preferably no more than ±5%, even more preferably no more than ±1%, and still more preferably no more than ±0.1% from the specified value, provided such variation is appropriate for the practice of the disclosed invention, although it should be understood that the value referred to by the modifier "about" is itself specifically disclosed.

[0018] The term "comprising" as used in the present specification and claims should not be interpreted as being limited to the means listed thereafter, nor does it exclude other elements or steps. It should be interpreted as specifying the presence of the mentioned features, integers, steps, or components as mentioned, but without excluding the presence or addition of one or more other features, integers, steps, or components, or groups thereof. Thus, the scope of the expression "a composition comprising components A and B" should not be limited to a composition consisting only of components A and B. It means that, in the context of the present invention, the only relevant components of the composition are A and B. Thus, the terms "comprising" and "including" encompass the more restrictive terms "consisting essentially of" and "consisting of."

[0019] "Positive electrode active material" is defined as a material that is electrochemically active in the positive electrode. An active material is understood to be a material that can capture and release Li ions when exposed to a voltage change over a period of time.

[0020] The following detailed description sets forth preferred embodiments in order to enable the practice of the invention. While the invention will be described with reference to these specific preferred embodiments, it will be understood that the following examples are intended to further clarify the invention and are not intended to limit the scope of the invention. The invention encompasses numerous alternatives, modifications, and equivalents that will be apparent from consideration of the following detailed description.

[0021] positive electrode active material In a first aspect, the present invention achieves the objectives by providing a cathode active material for a solid state rechargeable battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, characterized in that the cathode active material further comprises fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or more and 3.0 or less, as determined by XPS analysis, and carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, based on the total weight of the cathode active material, as determined by a carbon analyzer.

[0022] In a particularly preferred embodiment, this object is achieved by providing a positive electrode active material for the solid state rechargeable battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, further comprising: fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or more and 3.0 or less, as determined by XPS analysis; and carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, relative to the total weight of the positive electrode active material, as determined by a carbon analyzer.

[0023] Preferably, the active cathode material comprises at least 0.05 mol%, preferably at least 0.2 mol%, more preferably at least 0.5 mol%, and most preferably at least 0.7 mol% fluorine, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). Preferably, the active cathode material comprises at most 3.0 mol%, preferably at most 2.5 mol%, more preferably at most 2.0 mol%, and most preferably at most 1.8 mol% fluorine, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES. Preferably, the cathode active material contains fluorine in an amount of 0.05 mol% to 3.0 mol%, preferably 0.2 mol% to 2.5 mol%, more preferably 0.5 mol% to 2.0 mol%, and most preferably 0.7 mol% to 1.8 mol%, as determined by ICP-OES.

[0024] Preferably, the cathode active material contains aluminum in an amount of at least 0.01 mol%, preferably at least 0.05 mol%, more preferably at least 0.1 mol%, and most preferably at least 0.2 mol%, based on the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES. Preferably, the cathode active material contains aluminum in an amount of at most 2.0 mol%, preferably at most 1.5 mol%, more preferably at most 1.0 mol%, and most preferably at most 0.8 mol%, based on the total atomic content of Ni, Mn, and Co in the particles, as determined by ICP-OES. Preferably, the cathode active material contains aluminum in an amount of 0.01 mol% to 2.0 mol%, preferably 0.05 mol% to 1.5 mol%, more preferably 0.1 mol% to 1.0 mol%, and most preferably 0.2 mol% to 0.8 mol%, based on the total atomic content of Ni, Mn, and Co in the particles, as determined by ICP-OES.

[0025] In a preferred embodiment, the cathode active material has an atomic content of nickel of 55.0 mol % or greater and 95.0 mol % or less, preferably 58.0 mol % or greater and 90.0 mol % or less, and more preferably 60.0 mol % or greater and 88.0 mol % or less, based on the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

[0026] In a highly preferred embodiment, the cathode active material has an atomic content of nickel of 55.0 mol % to 75.0 mol %, preferably 60.0 mol % to 70.0 mol %, and more preferably 61.0 mol % to 68.0 mol %, based on the total atomic content of Ni, Mn, and Co in the material.

[0027] In a highly preferred embodiment, the cathode active material has an atomic content of nickel of 75.0 mol % to 95.0 mol %, preferably 78.0 mol % to 90.0 mol %, and more preferably 80.0 mol % to 88.0 mol %, based on the total atomic content of Ni, Mn, and Co in the material.

[0028] In a preferred embodiment, the cathode active material has an atomic content of cobalt of 0 to 40.0 mol%, preferably 2.0 to 20.0 mol%, more preferably 3.0 to 18.0 mol%, and most preferably 4.0 to 10.0 mol%, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

[0029] In a preferred embodiment, the material has an atomic content of manganese of 0 mol % to 40.0 mol %, preferably 2.0 mol % to 30.0 mol %, more preferably 3.0 mol % to 25.0 mol %, and most preferably 4.0 mol % to 10.0 mol %, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

[0030] As will be understood by those skilled in the art, the amounts of Li, Ni, Mn, Co, F, and Al are measured by ICP-OES. For example, and not by way of limitation, an Agilent ICP 720-ES is used in ICP-OES analysis. In the context of the present invention, the "atomic content" of a given element, which expresses its concentration, refers to the percentage of atoms of that element among all atoms in the compound. The notation "mol%" is equivalent to "mol percent" or "atomic percent." For example, and not by way of limitation, XPS analysis is performed using a Thermo K-α+ spectrometer (Thermo Scientific).

[0031] In a preferred embodiment, the cathode active material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at least 0.1, more preferably at least 0.15, and most preferably at least 0.2, as determined by XPS analysis. Preferably, the cathode active material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at most 2.5, more preferably at most 2.0, and most preferably at most 1.8, as determined by XPS analysis. Preferably, the cathode active material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at least 0.1 and at most 2.5, preferably at least 0.15 and at most 2.0, and most preferably at least 0.2 and at most 1.8, as determined by XPS analysis.

[0032] In a highly preferred embodiment, the active cathode material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at least 0.1, more preferably at least 0.15, and most preferably at least 0.2, as determined by XPS analysis. Preferably, the active cathode material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at most 0.8, more preferably at most 0.7, and most preferably at most 0.6, as determined by XPS analysis. Preferably, the active cathode material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of at least 0.1 and at most 0.8, preferably at least 0.15 and at most 0.7, and most preferably at least 0.15 and at most 0.6, as determined by XPS analysis.

[0033] In a preferred embodiment, the cathode active material comprises aluminum and has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at least 0.2, preferably at least 0.4, more preferably at least 0.5, and most preferably at least 0.6, as determined by XPS analysis. Preferably, the cathode active material has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at most 4.0, preferably at most 3.0, more preferably at most 2.0, and most preferably at most 1.5, as determined by XPS analysis. Preferably, the cathode active material has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at least 0.2 and at most 4.0, preferably at least 0.4 and at most 3.0, more preferably at least 0.5 and at most 2.0, and most preferably at least 0.6 and at most 1.5.

[0034] In a highly preferred embodiment, the active cathode material comprises aluminum and has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at least 0.2, preferably at least 0.5, more preferably at least 0.7, and most preferably at least 0.9, as determined by XPS analysis. Preferably, the active cathode material has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at most 1.35, preferably at most 1.30, more preferably at most 1.25, and most preferably at most 1.20, as determined by XPS analysis. Preferably, the active cathode material has an atomic ratio of Al to the total amount of Ni, Mn, and / or Co of at least 0.2 and at most 1.35, preferably at least 0.5 and at most 1.30, more preferably at most 0.7 and at most 1.25, and most preferably at least 0.9 and at most 1.20, as determined by XPS analysis.

[0035] In a preferred embodiment, the active cathode material has an Al to F ratio of at least 1.9, preferably at least 3, more preferably at least 4, where Al has an atomic ratio to the total amount of Ni, Mn, and / or C, as determined by XPS analysis, and F has an atomic ratio to the total amount of Ni, Mn, and / or Co, as determined by XPS analysis. In a preferred embodiment, the active cathode material has an Al to F ratio of at most 10, preferably at most 8, more preferably at most 6, where Al has an atomic ratio to the total amount of Ni, Mn, and / or C, as determined by XPS analysis, and F has an atomic ratio to the total amount of Ni, Mn, and / or Co, as determined by XPS analysis. In a preferred embodiment, the positive electrode active material has an Al to F ratio of 1.9 or greater and 10 or less, preferably 3 or greater and 8 or less, and more preferably 4 or greater and 6 or less, wherein Al has an atomic ratio relative to the total amount of Ni, Mn, and / or C, as determined by XPS analysis, and F has an atomic ratio relative to the total amount of Ni, Mn, and / or Co, as determined by XPS analysis.

[0036] XPS analysis provides the atomic content of an element in the top layer of a particle with a penetration depth of about 10 nm from the particle's periphery. The particle's periphery is also called the "surface." In the context of the present invention, atomic % means atomic percentage. As an expression of the concentration of a given element, atomic % or "atomic percent" means what percentage of all atoms in the compound are atoms of that element. The term atomic % is synonymous with mol % or "mole percent." For example, and not limiting to the present invention, XPS analysis is performed using a Thermo K-α+ spectrometer (Thermo Scientific).

[0037] In a preferred embodiment, the active cathode material comprises a carbon content of at least 500 ppm, more preferably at least 600 ppm, and most preferably at least 700 ppm, of the total weight of the active cathode material, as determined by a carbon analyzer. Preferably, the active cathode material comprises a carbon content of at most 3000 ppm, more preferably at most 2000 ppm, and most preferably at most 1500 ppm, of the total weight of the active cathode material, as determined by a carbon analyzer. Preferably, the active cathode material comprises a carbon content of at least 500 ppm and at most 3000 ppm, preferably at least 600 ppm and at most 2000 ppm, and more preferably at least 700 ppm and at most 1500 ppm, of the total weight of the active cathode material. As will be understood by those skilled in the art, the carbon content of the active cathode material of the present invention is measured by a carbon analyzer. For example, but not by way of limitation, the carbon content can be measured using a Horiba Emia-Expert carbon / sulfur analyzer.

[0038] In a preferred embodiment, the positive electrode material has a median particle size (d50 or D50) of 2.0 μm to 10.0 μm, as determined by laser diffraction. For example, and without limitation, the median particle size (d50 or D50) can be measured using a Malvern Mastersizer 3000. Preferably, the median particle size is 2.0 μm to 9.0 μm, more preferably 3.0 μm to 8.0 μm.

[0039] In a preferred embodiment, the positive electrode active material is a single crystal powder, or, in an equally preferred embodiment, the positive electrode active material is a polycrystalline powder.

[0040] The concept of single-crystal powder is well known in the art of cathode active materials. It refers to powders with predominantly single-crystalline particles. Such powders are a distinct type of powder compared to polycrystalline powders, which are made from predominantly polycrystalline particles. Those skilled in the art can easily distinguish between these two classes of powders based on microscopic images.

[0041] Single crystal particles are also known in the art as monolithic particles, integral particles or / and monocrystalline particles.

[0042] Although a technical definition of a single crystal powder is not necessary, as one skilled in the art can easily recognize such powders using an SEM, in the context of the present invention, a single crystal powder may be considered to be defined as a powder in which 80% or more of the particles by number are single crystal particles. This means that the powder has a size of at least 45 μm by at least 60 μm (i.e., at least 2700 μm). 2 ), preferably at least 100 μm×100 μm (i.e., at least 10,000 μm 2 ) can be determined on SEM images with a field of view.

[0043] A single crystal particle is either an individual crystal or a particle formed from fewer than five, preferably a maximum of three, primary particles that are themselves individual crystals. This can be observed by observing the grain boundaries with a suitable microscopic technique, such as a scanning electron microscope (SEM). Therefore, as will be appreciated by those skilled in the art, the determination of the median secondary particle diameter D50 is also applicable to single crystal powders.

[0044] In determining whether a particle is a single crystal particle, grains having a largest linear dimension observed by SEM that is smaller than 20% of the powder's median diameter D50 as determined by laser diffraction are ignored. This avoids inadvertently considering particles that are essentially single crystal but have some very small other grains, e.g., polycrystalline coatings deposited on them, as not being single crystal particles.

[0045] As will be appreciated by those skilled in the art, polycrystalline powders consist of secondary particles that include a plurality of primary particles, preferably greater than 20 primary particles, preferably greater than 10 primary particles, and most preferably greater than 5 primary particles.

[0046] In certain preferred embodiments, the present invention provides a cathode active material comprising single-crystal particles and having a median particle size D50 of 2.0 μm or greater and 10.0 μm or less, preferably 2.0 μm or greater and 9.0 μm or less, and more preferably 3.0 μm or greater and 8.0 μm or less, as determined by laser diffraction.

[0047] In certain preferred embodiments, the present invention provides a cathode active material comprising polycrystalline particles and having a median particle size D50 of 2.0 μm or greater and 10.0 μm or less, preferably 2.0 μm or greater and 9.0 μm or less, and more preferably 3.0 μm or greater and 8.0 μm or less, as determined by laser diffraction.

[0048] In a preferred embodiment, the fluorine source is an F-containing polymer, preferably an F-containing organic polymer, preferably polyvinylidene fluoride, or polytetrafluoroethylene (PTFE).

[0049] In a preferred embodiment, the fluorine-containing organic polymer is heated at a temperature of 200° C. to 350° C., preferably 250° C. to 300° C., for a period of 1 hour to 20 hours to obtain the positive electrode active material.

[0050] In a preferred embodiment, the positive electrode active material is a low leakage positive electrode active material.

[0051] In a further aspect, the present invention provides a secondary particle-based cathode active material for a solid state rechargeable battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, characterized in that the cathode active material further comprises: fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or more and 3.0 or less, as determined by XPS analysis; and carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, based on the total weight of the cathode active material, as determined by a carbon analyzer.

[0052] In a highly preferred embodiment of the secondary particle-based positive electrode active material, all embodiments relating to the positive electrode active material according to the first aspect of the present invention apply mutatis mutandis to the secondary particle-based positive electrode active material. For example, the various embodiments relating to the identities and amounts of Li, M', F, and Al described herein in the context of the positive electrode active material are equally applicable to the secondary particle-based positive electrode active material.

[0053] In a further aspect, the present invention provides a single-crystalline particle-based cathode active material for a solid state rechargeable battery comprising lithium, oxygen, nickel, and at least one metal selected from the group consisting of manganese and cobalt, characterized in that the cathode active material further comprises: fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or more and 3.0 or less, as determined by XPS analysis; and carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, based on the total weight of the cathode active material, as determined by a carbon analyzer.

[0054] In a highly preferred embodiment of a single-crystal particle-based active cathode material, all embodiments relating to the active cathode material according to the first aspect of the present invention apply mutatis mutandis to a single-crystal particle-based active cathode material. For example, the various embodiments relating to the identities and amounts of Li, M', F, and Al described herein in the context of the active cathode material are equally applicable to a secondary particle-based active cathode material.

[0055] Manufacturing method In a second aspect, the present invention also includes a method for producing an active cathode material, the method including the steps of mixing a lithium transition metal-based oxide compound, an F-containing polymer, and optionally an aluminum-containing powder, and heating the mixture at a temperature less than 350°C in an oxidizing atmosphere in a furnace for a time period of at least 1 hour and at most 20 hours to obtain the active cathode material.

[0056] A highly preferred embodiment is a method for producing an active cathode material, the active cathode material being according to the first aspect of the invention.

[0057] In a preferred embodiment of the present method, the lithium transition metal based oxide compound comprises Li, M' and oxygen, where M' comprises Ni, Mn, and Co.

[0058] In certain preferred embodiments, the lithium transition metal-based oxides used are also typically prepared according to a lithiation process, i.e., a process in which a mixture of a transition metal oxide precursor and a lithium source is heated, preferably at a temperature of at least 500° C. and up to 1000° C. Typically, the transition metal precursor is prepared by co-precipitation of one or more transition metal sources, such as salts, preferably sulfates or nitrates, more preferably sulfates, with the elements Ni, Mn, and / or Co, in the presence of an alkali compound, e.g., an alkali hydroxide, e.g., sodium hydroxide, and / or ammonia. Preferably, the lithium source is metallic lithium or a lithium salt, preferably a lithium salt such as LiOH.

[0059] In a preferred embodiment, the aluminum-containing powder comprises AI2O3.

[0060] Preferably, the F-containing polymer is an F-containing organic polymer, preferably polyvinylidene fluoride or polytetrafluoroethylene.

[0061] Preferably, the temperature at which the mixture is heated is 200°C or higher and 350°C or lower, preferably 250°C or higher and 300°C or lower.

[0062] In certain preferred embodiments, the mixture is heated for a period of more than 2 hours, preferably more than 3 hours, and more preferably more than 4 hours. In preferred embodiments, the mixture is heated for a period of less than 15 hours, preferably less than 12 hours, and preferably less than 10 hours. In preferred embodiments, the mixture is heated for a period of at least 2 hours and not more than 15 hours, preferably at least 3 hours and not more than 12 hours, and more preferably at least 4 hours and not more than 10 hours.

[0063] A preferred embodiment of the method is to heat the mixture, and the oxidizing atmosphere comprises or consists of oxygen, such as air.

[0064] Positive electrode active material obtained by this method In a third aspect, the present invention provides a cathode active material obtainable by the method according to the second aspect of the present invention.

[0065] As will be appreciated by those skilled in the art, all embodiments relating to the positive electrode active material according to the first aspect of the present invention and / or the method according to the second aspect of the present invention apply mutatis mutandis to a positive electrode active material obtainable by a method according to the present invention. For example, the various embodiments relating to the identities and amounts of F, Al, Ni, Mn, and Co described herein in the context of a positive electrode active material are equally applicable to a positive electrode active material obtainable by a method for the preparation of a positive electrode active material.

[0066] battery In a fourth aspect, the present invention relates to a battery comprising an active cathode material according to the first aspect of the invention and / or the third aspect of the invention.

[0067] In a preferred embodiment, the battery is a solid-state battery. Preferably, the solid-state battery comprises a polymer-based electrolyte. Preferably, the electrolyte is a polyethylene oxide-based solid electrolyte, more preferably, the electrolyte comprises polyethylene oxide.

[0068] Preferably, the solid-state battery further comprises an anode comprising an active anode material. Suitable electrochemically active anode materials are known in the art. For example, the anode may comprise graphitic carbon, metallic lithium, e.g., lithium foil, or a metal alloy containing lithium, such as a Li-In alloy, as the active anode material.

[0069] In a preferred embodiment, a battery according to the present invention comprises an active cathode material that is a polycrystalline material having a retention of at least 87%, preferably at least 88%, and most preferably at least 89%. Alternatively, in an equally preferred embodiment, a battery according to the present invention comprises an active cathode material that is a monocrystalline material having a retention of at least 98%, more preferably at least 99%, and most preferably at least 100%. As will be appreciated by those skilled in the art, battery retention is measured as described under Section 1.3.2 of the Examples.

[0070] In certain preferred embodiments, retention is

number

[0071] Step 1) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V, followed by a 10 minute rest.

[0072] Step 2) Discharge in constant current mode at a C rate of 0.05 with an end condition of 3.0 V, followed by a 10-minute rest. The discharge capacity of this step is DQ1.

[0073] Step 3) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V.

[0074] Step 4) Switch to constant voltage mode and maintain 4.4V for 60 hours.

[0075] Step 5) Discharge in constant current mode at a C rate of 0.05 with an end condition of 3.0 V. The discharge capacity of this step is DQ2.

[0076] In a preferred embodiment, the battery according to the present invention has a Q of less than 78 mAh / g, preferably less than 75 mAh / g, more preferably less than 70 mAh / g. total Alternatively, in an equally preferred embodiment, the battery according to the present invention comprises a positive electrode active material that is a polycrystalline material having a Q of less than 70 mAh / g, preferably less than 45 mAh / g, more preferably less than 40 mAh / g, even more preferably less than 32 mAh / g, and most preferably less than 32 mAh / g. total As will be appreciated by those skilled in the art, the Q of the battery total is measured as described under section 1.3.2 of the Examples.

[0077] In certain preferred embodiments, Q total is preferably defined as the total leakage capacitance at high voltage and temperature. In certain more preferred embodiments, Q total is defined as the total leakage capacitance at high voltage and high temperature in step 4) of the test method described below, and preferably Q total is defined by the coin cell test procedure in coin-shaped polymer cells cycled at 80°C using a Toscat-3100 computer-controlled constant current cycling station (Toyo Systems) using a 1C current definition of 160 mA / g in the metal window range of 3.0 V / Li to 4.4 V / Li, according to the following schedule:

[0078] Step 1) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V, followed by a 10 minute rest.

[0079] Step 2) Discharge in constant current mode at a C rate of 0.05 with an end condition of 3.0 V, followed by a 10-minute rest. The discharge capacity of this step is DQ1.

[0080] Step 3) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V.

[0081] Step 4) Switch to constant voltage mode and maintain 4.4V for 60 hours.

[0082] use In a fourth aspect, the present invention provides the use of a cathode active material according to the first aspect of the invention and / or the third aspect of the invention in a battery.

[0083] A preferred embodiment is the use of the cathode active material in a battery, preferably a solid-state battery, more preferably a polymer solid-state battery, to increase the battery's retention.

[0084] A preferred embodiment is the use of the cathode active material in a battery, preferably a solid-state battery, more preferably a sulfide solid-state battery, to reduce leakage of the battery.

[0085] In a fifth aspect, the present invention relates to the use of a battery according to the invention in any one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle or a hybrid electric vehicle, preferably in an electric vehicle or a hybrid electric vehicle. [Example]

[0086] 1. Explanation of analysis method 1.1.Inductively Coupled Plasma The composition of the positive electrode active material powder was measured by inductively coupled plasma (ICP) using an Agilent 720 ICP-OES. One gram of powder sample was dissolved in 50 mL of high-purity hydrochloric acid (at least 37 wt.% HCl based on the total weight of the solution) in an Erlenmeyer flask. The flask was covered with a watch glass and heated on a hot plate at 380 °C until the powder was completely dissolved. After cooling to room temperature, the solution from the Erlenmeyer flask was poured into a first 250 mL volumetric flask. The first volumetric flask was then filled to the 250 mL mark with deionized water, followed by a complete homogenization procedure (first dilution). An appropriate amount of solution was pipetted from the first volumetric flask and transferred to a second 250 mL volumetric flask for the second dilution. The second volumetric flask was filled to the 250 mL mark with internal standard elements and 10% hydrochloric acid, followed by homogenization. Finally, this solution was used for ICP measurement.

[0087] 1.2.Particle size distribution The particle size distribution (PSD) of the positive electrode active material powder was measured by laser diffraction particle size analysis using a Malvern Mastersizer 3000 equipped with a Hydro MV wet dispersion accessory after dispersing each powder sample in an aqueous medium. To improve the dispersion of the powder, sufficient ultrasonic irradiation and stirring were applied, and an appropriate surfactant was introduced. D50 was defined as the particle size at 50% of the cumulative volume percent distribution obtained from the Malvern Mastersizer 3000 using Hydro MV measurements.

[0088] 1.3.Polymer Cell Test 1.3.1. Preparation of polymer cells 1.3.1.1. Preparation of Solid Polymer Electrolyte (SPE) A solid polymer electrolyte (SPE) is prepared according to the following method.

[0089] Step 1) Polyethylene oxide (PEO, 1,000,000 g / mol, Alfa Aesar) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI, >98.0%, TCI) were mixed in 99.8 wt% anhydrous acetonitrile (Aldrich) using a mixer at 2000 revolutions per minute (rpm) for 30 minutes. The mass ratio of polyethylene oxide to LiTFSI was 3.0.

[0090] Step 2) Pour the mixture from step 1) into a Teflon dish and dry at 25°C for 12 hours.

[0091] Step 3) Remove the dried SPE from the dish and punch out the dried SPE to obtain an SPE disk with a thickness of 300 μm and a diameter of 19 mm.

[0092] 1.3.1.2. Preparation of the Positive Electrode The positive electrode is prepared according to the following process.

[0093] Step 1) Prepare a polymer electrolyte mixture containing a solution of polyethylene oxide (PEO, 100,000 g / mol, Alfa Aesar) in 99.7 wt% anhydrous anisole (Sigma-Aldrich) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI, >98.0%, TCI) in acetonitrile. The mixture has a weight ratio of PEO:LiTFSI of 74:26.

[0094] Step 2) The polymer electrolyte mixture prepared in step 1), the positive electrode active material, and the conductive powder (Super P, Timcal) are mixed in an acetonitrile solution in a weight ratio of 21:75:4 to prepare a slurry mixture. The mixture is mixed using a homogenizer at 5000 rpm for 45 minutes.

[0095] Step 3) Cast the slurry mixture from step 2) onto one side of a 20 μm thick aluminum foil with a coater gap of 100 μm.

[0096] Step 4) The foil onto which the slurry was cast is dried at 30° C. for 12 hours and then punched out to obtain catholyte electrodes with a diameter of 14 mm.

[0097] 1.3.1.3. Preparation of the negative electrode A Li foil (16 mm diameter, 500 μm thickness) is prepared as the negative electrode.

[0098] 1.3.1.4. Polymer Cell Assembly Assemble the coin-shaped polymer cell in an argon-filled glove box from bottom to top: 2032 coin cell can, positive electrode prepared in section 1.3.1.2, SPE prepared in section 1.3.1.1, gasket, negative electrode prepared in section 1.3.1.3, spacer, wave spring, and cell cap. Then, completely seal the coin cell to prevent electrolyte leakage.

[0099] Test Method Each coin-shaped polymer cell is cycled at 80°C using a Toscat-3100 computer-controlled constant current cycling station (Toyo Systems). The coin cell test procedure uses a 1C current definition of 160 mA / g in the metal window range of 3.0 V / Li to 4.4 V / Li, according to the following schedule:

[0100] Step 1) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V, followed by a 10 minute rest.

[0101] Step 2) Discharge in constant current mode at a C rate of 0.05 with an end condition of 3.0 V, followed by a 10-minute rest. The discharge capacity of this step is DQ1.

[0102] Step 3) Charge in constant current mode at a C rate of 0.05 with an end condition of 4.4V.

[0103] Step 4) Switch to constant voltage mode and maintain 4.4V for 60 hours.

[0104] Step 5) Discharge in constant current mode at a C rate of 0.05 with an end condition of 3.0 V. The discharge capacity of this step is DQ2.

[0105] Q total Q is defined as the total leakage capacitance at high voltage and temperature in step 4) of the described test method. total A small value indicates that the positive electrode active material powder is highly stable during high temperature operation.

[0106] Retention is

number

[0107] 1.4.X-ray photoelectron spectroscopy (XPS) In the present invention, X-ray photoelectron spectroscopy (XPS) is used to analyze the surface of the positive electrode active material powder particles. In XPS measurements, signals are obtained from the top of the sample, i.e., the first few nanometers (e.g., 1 nm to 10 nm) of the surface layer. Therefore, all elements measured by XPS are contained in the surface layer.

[0108] For surface analysis of the positive electrode active material powder particles, XPS measurements are performed using a Thermo K-α+ spectrometer. Monochromated Al Kα radiation (hυ = 1486.6 eV) is used with a 400 μm spot size and a 45° measurement angle. A broad survey scan to identify the elements present on the surface is performed with a pass energy of 200 eV. The C1s peak with maximum intensity (or center) at a binding energy of 284.8 eV is used as the calibration peak position after data collection. Then, for each identified element, at least 10 precise narrow scans at 50 eV are performed to determine the exact surface composition.

[0109] Curve fitting was performed in CasaXPS version 2.3.19PR1.0 using Shirley-type background processing and Scofield sensitivity coefficients, with fitting parameters according to Table 2a.

[0110] The lineshape GL(30) is the Gaussian / Lorentzian product formula for the 70% Gaussian and 30% Lorentzian lines. LA(α,β,m) is the asymmetric lineshape, where α and β define the tail broadening and m the width of the peak.

[0111] [Table 1]

[0112] For Al and Co peaks, limits are set for the peaks defined respectively according to Table 2b. All relevant Ni 3p peaks are not quantified.

[0113] [Table 2]

[0114] The surface content of Al and F, as determined by XPS, is expressed as the atomic fraction of Al and F, respectively, in the surface layer of the particle divided by the total content of Ni, Mn, and Co in that surface layer, and is calculated as follows:

[0115]

number

[0116]

number

[0117] 1.5.Carbon Analysis The carbon content of the cathode active material powder is measured using a Horiba Emia-Expert carbon / sulfur analyzer. 1 g of cathode active material powder is placed in a ceramic crucible in a high-frequency induction furnace. 1.5 g of tungsten and 0.2 g of tin as promoters are added to the crucible. The powder is heated at a programmable temperature, during which the gases produced during combustion are then analyzed by an infrared detector. The carbon concentration is determined by CO2 and CO2 analysis.

[0118] 2. Examples and Comparative Examples Comparative Example 1 A single crystalline positive electrode active material designated as CEX (Comparative Example) 1 was prepared according to the following steps.

[0119] Step 1) Preparation of transition metal oxide hydroxide precursor: Metal composition Ni 0.63 Mn 0.22 Co 0.15 A nickel-based transition metal oxide hydroxide powder (TMH1) with ##STR10## was prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) containing mixed nickel manganese cobalt sulfate, sodium hydroxide, and ammonia.

[0120] Step 2) First Mixing: TMH1 prepared in step 1) was mixed with Li2CO3 in an industrial blender to obtain a first mixture with a lithium to metal (Ni, Mn, and Co) ratio of 0.85.

[0121] Step 3) First heating: The first mixture from step 2) was heated at 900°C for 10 hours under a dry air atmosphere to obtain a first heating cake.

[0122] Step 4) Second Mixing: The first cooked cake from step 3) was mixed with LiOH in an industrial blender to obtain a second mixture with a lithium to metal (Ni, Mn, and Co) ratio of 1.05.

[0123] Step 5) Second heating: The second mixture from step 4) was heated at 950°C for 10 hours under dry air atmosphere, followed by wet milling, drying, and sieving to obtain the second heating product.

[0124] Step 6) Third Mixing: The second heating product from step 5) was mixed with 2 mol% Co from CO3O4 and 5 mol% Li from LiOH, relative to the total atomic contents of Ni, Mn, and Co, respectively, to obtain a third mixture.

[0125] Step 7) Third Heating: The third mixture from step 6) was heated at 775°C for 12 hours under dry air to obtain CEX1 containing Ni, Mn, and Co with a Ni:Mn:Co ratio of 0.61:0.22:0.17 as determined by ICP-OES. CEX1 has a D50 of 7 μm.

[0126] After wet milling in step 5), CEX1 is a single crystal powder.

[0127] Example 1 A single crystalline positive electrode active material designated EX (Example) 1 was prepared according to the following steps.

[0128] Step 1) Mixing: CEX1 was mixed with 3000 ppm of PTFE and 2000 ppm of alumina nanopowder in a mixer.

[0129] Step 2) Heating: The mixture obtained from step 1) was heated at 250° C. for 6 hours under an oxygen atmosphere, followed by milling to obtain EX1.

[0130] Comparative Example 2 A single crystalline positive electrode active material, designated CEX2.1, was prepared according to the following steps.

[0131] Step 1) Preparation of transition metal oxide hydroxide precursor: Metal composition Ni 0.86 Mn 0.07 Co 0.07Nickel-based transition metal oxide hydroxide powder (TMH2) with SiO2 was prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) containing mixed nickel manganese cobalt sulfate, sodium hydroxide, and ammonia.

[0132] Step 2) Oxidation of precursor: The TMH2 prepared in step 1) was heated at 400°C for 7 hours in an oxidizing atmosphere to obtain a heated product.

[0133] Step 3) First Mixing: The heated product prepared in step 2) was mixed with LiOH in an industrial blender to obtain a first mixture with a lithium to metal (Ni, Mn, and Co) ratio of 0.96.

[0134] Step 4) First heating: The first mixture from step 3) was heated at 890° C. for 11 hours under an oxidizing atmosphere to obtain a first heating product.

[0135] Step 5) Wet bead milling: The first-heated product from step 4) was bead milled in a solution containing 0.5 mol% Co relative to the total atomic content of Ni, Mn, and Co in the first-heated product, followed by drying and sieving to obtain a milled product. The weight ratio of solid to solution for bead milling was 6:4, and the bead milling was carried out for 20 minutes.

[0136] Step 6) Second mixing: The milled product obtained from step 5) was mixed in an industrial blender with 1.5 mol % Co from CO3O4, 0.25 mol % Zr from ZrO2, and 7.5 mol % Li from LiOH, each relative to the total atomic content of Ni, Mn, and Co in the milled product, to obtain a second mixture.

[0137] Step 7) Second Heating: The second mixture from step 6) was heated at 760°C for 10 hours under an oxidizing atmosphere, followed by grinding and sieving with the addition of 500 ppm Al from alumina (Al2O3) powder. The final product, CEX2.1, contains Ni, Mn, and Co with a Ni:Mn:Co ratio of 0.84:0.07:0.09 as determined by ICP-OES. CEX2.1 has a D50 of 4 μm.

[0138] A single crystalline positive electrode active material, designated CEX2.2, was prepared according to the following steps.

[0139] Step 1) Mixing: CEX2.1 was mixed with 3000 ppm PVDF and 2000 ppm alumina nanopowder in a mixer.

[0140] Step 2) Heating: The mixture obtained from step 1) was heated at 350° C. for 6 hours under an oxygen atmosphere, followed by milling to obtain CEX2.2.

[0141] CEX2.3 was prepared following the same method as CEX2.2, except that PTFE was used instead of PVDF in step 1).

[0142] CEX2.4 was prepared according to the same method as CEX2.2, except that PTFE was used instead of PVDF in step 1) and heating was performed at 450°C in step 2).

[0143] Example 2 A single crystalline positive electrode active material designated EX2.1 was prepared according to the following steps.

[0144] Step 1) Mixing: CEX2.1 was mixed with 3000 ppm PVDF and 2000 ppm alumina nanopowder in a mixer.

[0145] Step 2) Heating: The mixture obtained from step 1) was heated at 200° C. for 6 hours under an oxygen atmosphere, followed by milling to give EX2.1.

[0146] EX2.2 was prepared according to the same method as EX2.1, except that the heating temperature in step 2) was 250°C.

[0147] EX2.3 was prepared according to the same method as EX2.1, except that the heating temperature in step 2) was 300°C.

[0148] EX2.4 was prepared according to the same method as EX2.1, except that no alumina was added in step 1) and PTFE was used instead of PVDF, and no heating was performed in step 2).

[0149] EX2.5 was prepared according to the same method as EX2.1, except that no alumina was added in step 1) and PTFE was used instead of PVDF, and it was heated at 250°C in step 2).

[0150] EX2.6 was prepared following the same method as EX2.1, except that PTFE was used instead of PVDF in step 1) and no heating was performed in step 2).

[0151] EX2.7 was prepared following the same method as EX2.1, except that PTFE was used instead of PVDF in step 1).

[0152] EX2.8 was prepared according to the same method as EX2.1, except that PTFE was used instead of PVDF in step 1) and heating was performed at 250°C in step 2).

[0153] EX2.9 was prepared according to the same method as EX2.1, except that PTFE was used instead of PVDF in step 1) and heating was performed at 300°C in step 2).

[0154] Comparative Example 3 A single crystalline positive electrode active material, designated CEX3, was prepared according to the following steps.

[0155] Step 1) Preparation of transition metal oxide hydroxide precursor: Metal composition Ni 0.90 Mn 0.05 Co 0.05 Nickel-based transition metal oxide hydroxide powder (TMH3) with SiO2 was prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) containing mixed nickel manganese cobalt sulfate, sodium hydroxide, and ammonia.

[0156] Step 2) First Mixing: The TMH prepared in step 1) was mixed with LiOH and ZrO in an industrial blender to obtain a first mixture with a lithium to metal (Ni, Mn, and Co) ratio of 0.99 and 1000 ppm Zr.

[0157] Step 3) First heating: The first mixture from step 2) was heated at 890° C. for 11 hours under an oxidizing atmosphere to obtain a first heating product.

[0158] Step 4) Wet bead milling: The first-heated product from step 3) was bead milled in a solution containing 0.5 mol% Co relative to the total atomic content of Ni, Mn, and Co in the first-heated product, followed by drying and sieving to obtain a milled product. The weight ratio of solid to solution for bead milling was 6:4, and the bead milling was carried out for 20 minutes.

[0159] Step 5) Second Mixing: The milled product obtained from step 4) was mixed in an industrial blender with 1.5 mol% Co from CO3O4 and 1000 ppm Zr from ZrO2, relative to the total atomic content of Ni, Mn, and Co in the milled product, to obtain a second mixture.

[0160] Step 6) Second Heating: The second mixture from step 5) was heated at 760°C for 12 hours under an oxidizing atmosphere, followed by grinding and sieving with the addition of 500 ppm Al from alumina (Al2O3) powder. The product is CEX3, which contains Ni, Mn, and Co with a Ni:Mn:Co ratio of 0.88:0.05:0.07 as determined by ICP-OES. CEX3 has a D50 of 4 μm.

[0161] Example 3 A single crystalline positive electrode active material designated as EX3 was prepared according to the following steps.

[0162] Step 1) Mixing: CEX3 was mixed with 3000 ppm of PTFE and 2000 ppm of alumina nanopowder in a mixer.

[0163] Step 2) Heating: The mixture obtained from step 1) was heated at 250° C. for 6 hours under an oxygen atmosphere, followed by milling to obtain EX3.

[0164] Comparative Example 4 A polycrystalline positive electrode active material, designated CEX4, was prepared according to the following steps.

[0165] Step 1) Preparation of transition metal oxide hydroxide precursor: Metal composition Ni 0.83 Mn 0.12 Co 0.05 A nickel-based transition metal oxide hydroxide powder (TMH4) with SiO2 was prepared by a co-precipitation process in a large-scale continuous stirred tank reactor (CSTR) containing mixed nickel manganese cobalt sulfate, sodium hydroxide, and ammonia.

[0166] Step 2) First Mixing: The TMH4 prepared in step 1) was mixed with LiOH in an industrial blender to obtain a first mixture with a lithium to metal (Ni, Mn, and Co) ratio of 0.975.

[0167] Step 3) First heating: The first mixture from step 2) was heated at 765°C for 10 hours under an oxidizing atmosphere to obtain a first heating product, which was then crushed and sieved.

[0168] Step 4) Second mixing: The first heating product from step 3) and LiOH as a lithium source were homogeneously mixed in an industrial blending device with a lithium to metal (Ni, Mn, and Co) ratio of 1.03 to obtain a second mixture.

[0169] Step 5) Second heating: The second mixture from step 4) was heated at 770°C for 12 hours under oxygen atmosphere to obtain CEX4 containing Ni, Mn, and Co with a Ni:Mn:Co ratio of 0.83:0.12:0.05 as determined by ICP-OES. CEX4 has a D50 of 6 μm.

[0170] Example 4 A polycrystalline positive electrode active material designated EX4.1 was prepared according to the following steps.

[0171] Step 1) Mixing: CEX4 was mixed with 2000 ppm PTFE and 2000 ppm alumina nanopowder in a mixer.

[0172] Step 2) Heating: The mixture obtained from step 1) was heated at 250° C. for 6 hours under an oxygen atmosphere, followed by milling to give EX4.1.

[0173] EX4.2 was prepared according to EX4.1 except that 3000 ppm of PTFE was used in step 1).

[0174] EX4.3 was prepared according to EX4.1 except that 4000 ppm of PTFE was used in step 1).

[0175] [Table 3]

[0176] Table 2 summarizes the compositions of the examples and comparative examples and their corresponding electrochemical properties.

[0177] CEX1 and EX1 are single crystal positive electrode active materials containing approximately 61 mol% Ni. EX1, which further contains F and Al, has a higher Q than CEX1. total This results in lower blood pressure and improved retention.

[0178] CEX2.1 to CEX2.5 and EX2.1 to EX2.9 are single crystal positive electrode active materials containing approximately 84 mol% Ni. CEX2.1 is a positive electrode active material that does not contain F. CEX2.2 to CEX2.4 are mixtures of CEX2.1 and an F-containing polymer, either PVDF or PTFE, which are heated to a temperature of 350°C or higher. Such heat treatment results in the formation of Q total It can be seen that positive electrode active materials with high carbon content and low retention are obtained. Due to the low carbon content of less than 350 ppm, the F-containing polymer is likely to decompose at temperatures ≥ 350°C. On the other hand, EX2.1 to EX2.9 are heat-treated at temperatures ≤ 300°C. All of these examples show improved electrochemical properties compared to CEX2.1 to CEX2.4.

[0179] CEX3 and EX3 are single-crystal cathode active materials containing approximately 88 mol% Ni. EX3, which contains F and Al, has improved electrochemical properties compared to CEX3.

[0180] CEX4 and EX4.1-EX4.3 are polycrystalline cathode active materials containing approximately 88 mol% Ni. EX4.1-EX4.3 are obtained from CEX4 mixed with alumina and various amounts of PTFE and heated at 250°C. EX4 exhibits lower Qtotal and higher retention compared to CEX4.

[0181] Table 2 also summarizes the XPS analysis results for CEX2.3, CEX2.4, EX2.6, EX2.7, EX2.8, and EX2.9, showing the Al and F fractions relative to the total atomic fractions of Ni, Mn, and Co. Values ​​greater than 0 indicate the presence of Al or F at the surface of the positive electrode active material, relative to XPS measurements that acquire signals from the top of the sample, i.e., the first few nanometers (e.g., 1 nm to 10 nm) of the surface layer.

[0182] It is concluded that the positive electrode active material containing F and C is suitable for achieving the objectives of the present invention, i.e., low total leakage capacity (Q total ) and high retention, providing a positive electrode active material with good electrochemical properties.

Claims

1. A positive electrode active material for a solid state rechargeable battery comprising lithium, oxygen, nickel, zirconium, and at least one metal selected from the group consisting of manganese and cobalt, fluorine, wherein the atomic ratio of F to the total amount of Ni, Mn, and / or Co is 0.05 or greater and 3.0 or less, as determined by XPS analysis; 1. A positive electrode active material, further comprising: carbon, wherein the carbon content is 370 ppm or more and 5000 ppm or less, based on a total weight of the positive electrode active material, as determined by a carbon analyzer.

2. 2. The cathode active material according to claim 1, wherein the cathode active material has an atomic ratio of F to the total amount of Ni, Mn, and / or Co of 0.1 or more and 2.5 or less, as determined by XPS analysis.

3. 10. The active cathode material of claim 1, wherein the active cathode material comprises carbon having a carbon content greater than 500 ppm and less than 3000 ppm as determined by a carbon analyzer.

4. 2. The cathode active material of claim 1, comprising aluminum, wherein the atomic ratio of Al to the total amount of Ni, Mn, and / or Co is 0.2 or more and 4.0 or less as determined by XPS analysis.

5. 10. The cathode active material of claim 1, comprising aluminum in an amount of 0.01 mol % or more and 2.0 mol % or less, based on the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

6. 2. The cathode active material of claim 1, wherein the cathode active material has an atomic content of nickel of 55.0 mol % or greater and 95.0 mol % or less, preferably 58.0 mol % or greater and 90.0 mol % or less, based on the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

7. 2. The cathode active material of claim 1, wherein the cathode active material has an atomic content of cobalt of greater than or equal to 0 mol % and less than or equal to 40.0 mol %, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

8. 2. The cathode active material of claim 1, wherein the cathode active material has an atomic content of manganese of greater than or equal to 0 mol % and less than or equal to 40.0 mol %, relative to the total atomic content of Ni, Mn, and Co in the material, as determined by ICP-OES.

9. The cathode active material of claim 1 , wherein the cathode active material comprises single-crystal particles.

10. The particles have a median particle size D50 of 2.0 μm or greater and 10.0 μm or less, as determined by laser diffraction particle size analysis. Ａ The positive electrode active material according to claim 9 , having

11. The cathode active material of claim 1 , wherein the cathode active material comprises polycrystalline particles.

12. The particles have a median particle size D50 of 2.0 μm or greater and 10.0 μm or less, as determined by laser diffraction particle size analysis. Ａ The positive electrode active material according to claim 11 , having

13. A method for producing a positive electrode active material, mixing a lithium transition metal oxide compound containing zirconium with an F-containing polymer; and heating the mixture in an oxidizing atmosphere in a furnace at a temperature less than 350° C. for a time period of 1 hour to 20 hours to obtain the positive electrode active material; the positive electrode active material contains carbon, the carbon content is greater than or equal to 370 ppm and less than or equal to 5000 ppm, based on the total weight of the positive electrode active material, as determined by a carbon analyzer.

14. 14. The method of claim 13, wherein the F-containing polymer is polyvinylidene fluoride or polytetrafluoroethylene.

15. The method according to claim 13 or 14, wherein the heating temperature is 200°C or higher and lower than 350°C.

16. The method of claim 13, wherein the positive electrode active material is according to any one of claims 1 to 9.

17. A solid-state battery comprising the positive electrode active material according to any one of claims 1 to 12.

18. 20. Use of the solid-state rechargeable battery of claim 17 in any one of a portable computer, a tablet, a mobile phone, an energy storage system, an electric vehicle, or a hybrid vehicle.

19. The method of claim 13, wherein the oxidizing atmosphere consists of oxygen.

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