WO2022089205A1 - 一种掺杂型高镍三元材料及其制备方法 - Google Patents

一种掺杂型高镍三元材料及其制备方法 Download PDF

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WO2022089205A1
WO2022089205A1 PCT/CN2021/123411 CN2021123411W WO2022089205A1 WO 2022089205 A1 WO2022089205 A1 WO 2022089205A1 CN 2021123411 W CN2021123411 W CN 2021123411W WO 2022089205 A1 WO2022089205 A1 WO 2022089205A1
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solution
nickel ternary
nickel
source
ternary material
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French (fr)
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杜少林
余海军
谢英豪
张学梅
明帮来
候彭
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to EP21884934.7A priority Critical patent/EP4234498A4/en
Publication of WO2022089205A1 publication Critical patent/WO2022089205A1/zh
Priority to US18/139,947 priority patent/US20230264975A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C01P2002/54—Solid solutions containing elements as dopants one element only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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 disclosure belongs to the field of battery materials, and in particular relates to a doped high-nickel ternary material and a preparation method thereof.
  • Lithium-ion battery materials are widely used as energy storage devices for portable electronic devices and power vehicles due to their high energy density, long service life, small self-discharge, no memory effect, and environmental protection.
  • the cathode material is the most critical part of the lithium-ion battery, and its cost accounts for about one-third of the entire battery.
  • the lithium ions in the positive electrode material are the only source to maintain the normal operation of the lithium battery, so the energy density of the positive electrode material largely determines the energy density of a battery.
  • the commonly used cathode materials for lithium ion batteries are polyanionic material LiFePO 4 , layered material LiCoO 2 and layered ternary material LiNi x Co y Mn z O 2 .
  • ternary materials have attracted much attention due to their high energy density, high voltage platform, and high specific capacity.
  • the content of nickel in the ternary material has a great influence on its electrochemical performance.
  • the specific performance is that the higher the nickel content, the higher the energy density and the higher the capacity.
  • the development of ternary materials with high nickel content has become a research hotspot nowadays.
  • high-nickel ternary materials have many disadvantages, such as the decrease in electrochemical performance caused by cation mixing, the decrease in thermal stability and poor electrical conductivity due to the high nickel content, and the unstable surface structure.
  • the resulting battery has serious polarization, rapid capacity decay, material failure caused by volume effect, and electrochemical performance degradation caused by excessive surface alkali content.
  • these problems will become more obvious, which seriously hinders the application scale of ternary materials.
  • ternary materials In order to solve the shortcomings of ternary materials, a lot of research work has been done. Studies have shown that the formation of cracks in ternary material microspheres during battery charge and discharge cycles can be solved by element doping. Commonly used doping elements include Al, Zr, Mn, Nb, etc.
  • the high-nickel ternary material shows good cycle stability. However, in this method, the surface of the lithiated precursor of the high-nickel ternary material is coated with manganese/aluminum oxide, and then the target material is obtained by calcination, which cannot guarantee the uniform distribution of doping elements in the material.
  • Another example is the preparation method of an aluminum-doped NCM622-type high-nickel ternary material.
  • the present disclosure provides a doped high-nickel ternary material and a preparation method thereof.
  • the doped high-nickel ternary material synthesized by the preparation method has the advantages of high capacity and long service life.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • the doping element is Zr, Nb, Al, F, Mn, La at least one.
  • the nickel source, cobalt source, and manganese source are nickel nitrate hexahydrate, cobalt nitrate hexahydrate, and manganese acetate tetrahydrate.
  • the molar ratio of the nickel source, the cobalt source, and the manganese source is (0.6-0.9):(0.05-0.2):(0.05-0.2).
  • the molar ratio of the nickel source, the cobalt source, and the manganese source is 0.8:0.1:0.1 or 0.6:0.2:0.2.
  • the solvent is water.
  • the total concentration of metal ions in the solution A is 1-1.5 mol/L.
  • the oxidant is at least one of sodium persulfate, sodium peroxide or ammonium persulfate.
  • the doping element is added to solution A in the form of nitrate, phosphate or sulfate.
  • the total content of the doping element in solution B is 0.01-0.05 mol/L.
  • the complexing agent is an acrylic acid solution.
  • step (2) the added amount of the complexing agent is 50-150 mL.
  • step (2) the amount of nitric acid added is 5-15 mL.
  • the drying temperature is 120°C-180°C, and the drying time is 4-8h.
  • step (4) the temperature of the first sintering is 150°C-250°C, and the time of the first sintering is 1-3 h.
  • the atmosphere of the first sintering is air or oxygen, and the oxygen flow rate is 0.2-0.4 mL/min.
  • step (4) the temperature of the second sintering is 400° C.-600° C., and the time of the second sintering is 4-8 h.
  • the atmosphere of the second sintering is air or oxygen.
  • the lithium source is lithium carbonate or lithium hydroxide.
  • step (5) the amount of lithium ions in the lithium source is 0.2-0.25 mol.
  • the calcination temperature is 600°C-900°C, and the calcination time is 8-16 h.
  • the calcining atmosphere is oxygen, and the oxygen flow rate is 0.2-0.4 mL/min.
  • the mesh used in the sieving is 325-400 mesh.
  • the above preparation method firstly synthesizes the high nickel ternary material precursor through the method of thermal polymerization of acrylic acid, in the process adding sodium persulfate (oxidant) and doping elements, the product is placed in a tube furnace after filtering, drying and grinding Low temperature and high temperature calcination is carried out, and oxygen is slowly introduced into the calcination process.
  • the calcined doped high-nickel ternary precursor is ground and mixed with a lithium source, and the doped high-nickel ternary material is synthesized by a high-temperature solid-phase method.
  • the addition of sodium persulfate (oxidant) and the low-temperature pre-oxidation process increase the average valence state of nickel in the ternary precursor, reduce the presence of positive divalent nickel ions, eliminate the crystal defects of the ternary material, and then reduce the degree of cation mixing, Improve the cycle stability of the material. Secondary sintering can effectively reduce the alkali content on the surface of the material, reduce the polarization reaction of the battery, and improve the conductivity and cycle life of the material.
  • the addition of doping elements improves the thermal stability of the material, suppresses the capacity decay during cycling, and improves the cycling stability and cycle life of the material.
  • the doped high nickel ternary material synthesized by this method has the advantages of high capacity and long life.
  • the reversible capacity of the doped high nickel ternary material reaches 181-193 mAh/g for the first time at a current of 0.2 C.
  • a lithium battery includes the doped high nickel ternary material.
  • sodium persulfate is added in the preparation of the doped high-nickel ternary precursor.
  • Sodium persulfate has strong oxidizing properties, which can improve the average valence of nickel in the high-nickel ternary precursor and alleviate the cationic The capacity fading problem caused by shuffling.
  • secondary sintering is used in the preparation of the doped high-nickel ternary precursor.
  • low-temperature pre-sintering is used, and then high-temperature sintering is used.
  • This method can effectively reduce the surface alkali content of the material and increase the material
  • the conductivity of the battery reduces the polarization of the battery, thereby improving the conductivity and cycle life of the material.
  • Doping elements are added in the preparation of doped high-nickel ternary precursors in the embodiments of the present disclosure, and the addition of doping elements can effectively improve the thermal stability of high-nickel ternary materials, thereby improving the safety performance of the materials and cycle life.
  • the high-nickel ternary material prepared in the embodiment of the present disclosure is prepared from a doped high-nickel ternary precursor that has undergone sodium sulfate (oxidant) and secondary sintering, and the doped high-nickel ternary material prepared by this method In addition to high specific capacity and long cycle life, the ternary material still exhibits high specific capacity and long cycle life at high temperature.
  • Example 1 is a graph of the cycle performance of the materials prepared in Example 1 and Comparative Example 1 of the present disclosure at a current density of 0.2C;
  • FIG. 2 is a SEM image of the doped high-nickel ternary material prepared in Example 1 of the present disclosure.
  • the conventional conditions or the conditions suggested by the manufacturer are used.
  • the raw materials, reagents, etc., which are not specified by the manufacturer, are all conventional products that can be purchased from the market.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1 (lithium
  • the amount of lithium ions in the source is 0.2-0.25 mol)
  • kept at 750° C. for 12 hours in an oxygen atmosphere and after annealing, ground and passed through a 325-mesh sieve to obtain a doped high-nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 193mAh/g for the first time under the current of 0.2C.
  • the doped high-nickel ternary material prepared above shows excellent electrochemical performance as a positive electrode material for lithium-ion batteries, with a reversible capacity of 193mAh/g for the first time at a current of 0.2C, and a reversible capacity after 300 charge-discharge cycles. There is still 180mAh/g, and the reversible capacity is still 161mAh/g after 200 charge-discharge cycles at a current of 5C. The battery was tested for cycle performance at 70°C, and the reversible capacity was still 173mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1, in In an oxygen atmosphere at 750°C for 12 hours, annealing, grinding and passing through a 325 mesh sieve to obtain a doped high nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 184mAh/g for the first time under the current of 0.2C.
  • the doped high-nickel ternary material prepared above shows excellent electrochemical performance as a positive electrode material for lithium-ion batteries. After 300 charge-discharge cycles at a current of 0.2C, the reversible capacity is still 166mAh/g, and at 5C The reversible capacity is still 146mAh/g after 200 charge-discharge cycles at the same current. The battery was tested for cycle performance at 70°C, and the reversible capacity was still 163mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 186mAh/g for the first time under the current of 0.2C.
  • the doped high-nickel ternary material prepared above shows excellent electrochemical performance as a positive electrode material for lithium-ion batteries, and the reversible capacity is still 170mAh/g after 300 charge-discharge cycles at a current of 0.2C.
  • the reversible capacity is still 128mAh/g after 200 charge-discharge cycles at the same current.
  • the battery was tested for cycle performance at 70°C, and the reversible capacity was still 158mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • a doped high nickel ternary material the chemical formula is LiNi 0.799 Co 0.1 Mn 0.1 NbLa 0.001 O 2 , and the reversible capacity reaches 183mAh/g for the first time under the current of 0.2C.
  • the doped high-nickel ternary material prepared above shows excellent electrochemical performance as a positive electrode material for lithium-ion batteries. After 300 charge-discharge cycles at a current of 0.2C, the reversible capacity is still 165mAh/g, and at 5C The reversible capacity is still 133mAh/g after 200 charge-discharge cycles at the same current. The battery was tested for cycle performance at 70°C, and the reversible capacity was still 133mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • a doped high nickel ternary material the chemical formula is LiNi 0.7999 Co 0.1 Mn 0.1 NbLa 0.0001 O 2 , and the reversible capacity reaches 181mAh/g for the first time under the current of 0.2C.
  • the above-prepared doped high-nickel ternary material showed excellent electrochemical performance as a positive electrode material for lithium-ion batteries.
  • the reversible capacity was still 164mAh/g, and at 5C
  • the reversible capacity is still 139mAh/g after 200 charge-discharge cycles at the same current.
  • the battery was tested for cycle performance at 70°C, and the reversible capacity was still 142mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1.
  • the temperature is kept at 600°C for 8 hours, annealed, ground and passed through a 325-mesh sieve to obtain a doped high-nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 182mAh/g for the first time under the current of 0.2C.
  • the high-nickel ternary material prepared above is used as a positive electrode material for lithium-ion batteries.
  • the reversible capacity is 159mAh/g after 300 charge-discharge cycles at a current of 0.2C, and the reversible capacity after 200 charge-discharge cycles at a current of 5C. There are 135mAh/g.
  • the battery was tested for cycle performance at 70°C, and the reversible capacity was 123mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a doped high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1.
  • the temperature is kept at 900°C for 16h, annealed, ground and passed through a 325-mesh sieve to obtain a doped high-nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 187mAh/g for the first time under the current of 0.2C.
  • the high-nickel ternary material prepared above is used as a positive electrode material for lithium-ion batteries.
  • the reversible capacity is 168mAh/g after 300 charge-discharge cycles at a current of 0.2C, and the reversible capacity after 200 charge-discharge cycles at a current of 5C. There are 135mAh/g.
  • the battery was tested for cycle performance at 70°C, and the reversible capacity was 133mAh/g after 200 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a high-nickel ternary material comprising the following steps:
  • Solution A is prepared by mixing sodium persulfate solution with a concentration of 0.1 mol/L and 100 mL of ammonia solution with A and fully stirring to obtain mixed solution B;
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1, in an oxygen atmosphere Heat preservation at 700°C for 12h, fully grind after annealing and pass through a 325-mesh sieve to obtain a high nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the reversible capacity reaches 162mAh/g for the first time under the current of 0.2C.
  • the high-nickel ternary material prepared in Comparative Example 1 was used as a positive electrode material for lithium-ion batteries. After 100 charge-discharge cycles at 0.2C, the reversible capacity was 83mAh/g, and after 100 charge-discharge cycles at 5C The reversible capacity is 60mAh/g. The battery was tested for cycle performance at 70°C, and the reversible capacity was still 68mAh/g after 100 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1.
  • an oxygen atmosphere at 700°C for 12 hours after annealing, it is fully ground and passed through a 325-mesh sieve to obtain a doped high-nickel ternary material.
  • a doped high nickel ternary material the chemical formula is LiNi 0.797 Co 0.1 Mn 0.1 NbLa 0.003 O 2 , and the reversible capacity reaches 158mAh/g for the first time under the current of 0.2C.
  • the high-nickel ternary material prepared in Comparative Example 2 was used as a positive electrode material for lithium-ion batteries. After 100 charge-discharge cycles at 0.2C, the reversible capacity was 95mAh/g, and at 5C after 100 charge-discharge cycles The reversible capacity is 63mAh/g. The battery was tested for cycle performance at 70°C, and the reversible capacity was still 78mAh/g after 100 charge-discharge cycles at a current of 0.1C.
  • a preparation method of a high-nickel ternary material comprising the following steps:
  • the stoichiometric ratio of the content of lithium in the lithium source to the total content of metal ions in the solution A prepared in step (1) is 1.06:1, in an oxygen atmosphere Heat preservation at 700°C for 12h, fully grind after annealing and pass through a 325 mesh sieve to obtain a high nickel ternary material.
  • a doped high nickel ternary material, the chemical formula is LiNi 0.8 Co 0.1 Mn 0.1 O 2 , and the reversible capacity reaches 152mAh/g for the first time under the current of 0.2C.
  • the high-nickel ternary material prepared in Comparative Example 3 is used as a positive electrode material for lithium-ion batteries.
  • the reversible capacity is 89mAh/g after 100 charge-discharge cycles at a current of 0.2C, and reversible after 100 charge-discharge cycles at a current of 5C.
  • the capacity is 69mAh/g.
  • the battery was tested for cycle performance at 70°C, and the reversible capacity was still 73mAh/g after 100 charge-discharge cycles at a current of 0.1C.
  • a doped high-nickel ternary material and a preparation method thereof provided by the embodiments of the present disclosure have been described in detail above.
  • the principles and implementations of the present disclosure are described by specific embodiments herein.
  • the above embodiments describe It is merely intended to assist in an understanding of the disclosed methods and their core ideas, including several embodiments, and also to enable any person skilled in the art to practice the present disclosure, including making and using any devices or systems, and implementing any incorporated methods. It should be pointed out that for those skilled in the art, without departing from the principles of the present disclosure, several improvements and modifications can also be made to the present disclosure, and these improvements and modifications also fall within the protection scope of the claims of the present disclosure.

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Abstract

本公开属于电池材料领域，公开了一种掺杂型高镍三元材料及其制备方法，该制备方法包括以下步骤：(1)将镍源、钴源、锰源溶于溶剂中，混合得到溶液A，再加入氧化剂和掺杂元素，搅拌，得到溶液B；(2)将络合剂、硝酸加入溶液B，搅拌，得到溶液C；(3)将溶液C烘干，得到气凝胶D；(4)将气凝胶D研磨，进行低温预烧，再继续升温进行第一次煅烧，得到前驱体粉末E；(5)将前驱体粉末E与锂源混合，进行第二次煅烧，研磨，过筛即得掺杂型高镍三元材料。本公开在制备掺杂型高镍三元前驱体时加入了过硫酸钠，过硫酸钠具有强氧化性，可以提高高镍三元前驱体中镍的平均价态，缓解阳离子混排造成的容量衰减问题。

Description

一种掺杂型高镍三元材料及其制备方法 技术领域
本公开属于电池材料领域，具体涉及一种掺杂型高镍三元材料及其制备方法。
背景技术
锂离子电池材料由于具有能量密度高、使用寿命长、自放电程度小、无记忆效应及环保等优势被广泛用作便携式电子设备及动力汽车的储能器件。正极材料是锂离子电池中最为关键的一部分，其成本大约占据了整个电池的三分之一。正极材料中的锂离子是维持锂电池正常工作的唯一来源，因此正极材料的能量密度在很大程度上决定了一个电池的能量密度。
目前常用的锂离子电池正极材料为聚阴离子型材料LiFePO 4、层状材料LiCoO 2以及层状三元材料LiNi xCo yMn zO 2。与其他材料相比，三元材料由于具有能量密度高、电压平台高、比容量高等优点而备受关注。三元材料中镍的含量对其电化学性能影响较大，具体表现为镍含量越高，能量密度越高，容量越高。为满足人们对长续航、大容量锂离子电池的需求，开发具有较高镍含量的三元材料成为时下的研究热点。但是，高镍三元材料有很多的缺点，比如阳离子混排带来的电化学性能下降，由于镍含量较高而随之产生的热稳定性降低及较差的导电性，表面结构不稳定带来的电池极化严重、容量快速衰减，体积效应导致的材料失效以及表面碱含量过高导致的电化学性能下降等问题。随着三元材料中镍含量的增加，这些问题会更加明显，严重阻碍了三元材料的应用规模。
为解决三元材料的缺点，人们做了大量的研究工作。研究表明，通过元素掺杂可以解决三元材料微球在电池充放电循环过程中裂纹的产生，常用的掺杂元素有Al、Zr、Mn、Nb等，如采用锰、铝掺杂高镍三元材料，使高镍三元材料表现出了很好的循环稳定性。但是该方法是将锰/铝氧化物包覆在高镍三元材料的锂化前驱体表面，之后再通过煅烧得到目标材料，无法保证掺杂元素在材料中均匀分布。又如利用一种铝元素掺杂NCM622型高镍三元材料的制备方法，在配锂时，加入氢氧化铝与前驱体和锂盐混合均匀，之后煅烧得到铝元素掺杂NCM622型高镍三元材料，通过掺杂改性，可有效提高高镍三元材料的结构稳定性，改善材料的倍率性能和循环性能，但这种制备方法采用干法直接将铝盐与前驱体研磨，掺杂的准确性和均匀性得不到保障，掺杂的效果不佳。除了掺杂元素之外，缓解Li +与Ni 2+混排，即如何提高材料中镍的平均价态成为提高高镍三元材料性能的新突破口。
发明内容
本公开提供一种掺杂型高镍三元材料及其制备方法，通过该制备方法合成的掺杂型高镍三元材料具有容量高、寿命长的优点。
有鉴于此，本公开采用以下技术方案：
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)将镍源、钴源、锰源溶于溶剂中，混合得到溶液A，再加入氧化剂和掺杂元素，搅拌，得到溶液B；
(2)将络合剂、硝酸加入溶液B，搅拌，得到溶液C；
(3)将溶液C烘干，得到气凝胶D；
(4)将气凝胶D研磨，进行第一次烧结，再继续进行第二次烧结，得到前驱体粉末E；
(5)将前驱体粉末E与锂源混合，进行煅烧，研磨，过筛即得掺杂型高镍三元材料；所述掺杂元素为Zr、Nb、Al、F、Mn、La中的至少一种。
在一些实施例中，步骤(1)中，所述镍源、钴源、锰源为六水合硝酸镍、六水合硝酸钴、四水合醋酸锰。
在一些实施例中，步骤(1)中，所述镍源、钴源、锰源的摩尔比为(0.6-0.9)：(0.05-0.2)：(0.05-0.2)。
在另一实施例中，步骤(1)中，所述镍源、钴源、锰源的摩尔比为0.8:0.1:0.1或0.6:0.2:0.2。
在一些实施例中，步骤(1)中，所述溶剂为水。
在一些实施例中，步骤(1)中，所述溶液A中金属离子总浓度为1-1.5mol/L。
在一些实施例中，步骤(1)中，所述氧化剂为过硫酸钠、过氧化钠或过硫酸铵中的至少一种。
在一些实施例中，步骤(1)中，所述掺杂元素是配置成硝酸盐、磷酸盐或硫酸盐的形式添加到溶液A中。
在一些实施例中，步骤(1)中，所述掺杂元素占溶液B中总含量为0.01-0.05mol/L。
在一些实施例中，步骤(2)中，所述络合剂为丙烯酸溶液。
在一些实施例中，步骤(2)中，所述络合剂的添加量为50-150mL。
在一些实施例中，步骤(2)中，所述硝酸添加量为5-15mL。
在一些实施例中，步骤(3)中，所述烘干的温度为120℃-180℃，烘干的时间为4-8h。
在一些实施例中，步骤(4)中，所述第一次烧结的温度为150℃-250℃，第一次烧结的 时间为1-3h。
在一些实施例中，步骤(4)中，所述第一次烧结的气氛为空气或氧气，所述氧气流速为0.2-0.4mL/min。
在一些实施例中，步骤(4)中，所述第二次烧结的温度为400℃-600℃，第二次烧结的时间为4-8h。
在一些实施例中，步骤(4)中，所述第二次烧结的气氛为空气或氧气。
在一些实施例中，步骤(5)中，所述锂源为碳酸锂或氢氧化锂。
在一些实施例中，步骤(5)中，所述锂源中锂离子的量为0.2-0.25mol。
在一些实施例中，步骤(5)中，所述煅烧的温度为600℃-900℃，煅烧的时间为8-16h。
在一些实施例中，步骤(5)中，所述煅烧的气氛为氧气，所述氧气流速为0.2-0.4mL/min。
在一些实施例中，步骤(5)中，所述过筛使用的目数为325-400目。
原理：
上述制备方法首先通过丙烯酸热聚合的方法合成高镍三元材料前驱体，在该过程中加入过硫酸钠(氧化剂)以及掺杂元素，产物经过滤、烘干及研磨后置于管式炉中进行低温、高温煅烧，煅烧过程缓慢通入氧气。煅烧后的掺杂型高镍三元前驱体经研磨后与锂源混合，通过高温固相法合成掺杂型高镍三元材料。过硫酸钠(氧化剂)的加入及低温预氧化过程提高了三元前驱体中镍的平均价态，减少正二价镍离子的存在，消除三元材料的晶体缺陷，进而减少阳离子混排的程度，提高材料的循环稳定性。二次烧结可以有效的降低材料表面的碱含量，减少电池的极化反应，提高材料的导电性及循环寿命。掺杂元素的加入提高了材料的热稳定性，抑制循环过程中的容量衰减，提升了材料的循环稳定性与循环寿命。通过该法合成的掺杂型高镍三元材料具有容量高、寿命长的优点。
一种掺杂型高镍三元材料，由上述方法制得，其化学式为LiNi xCo yMn zM iO 2，其中0.6≦x≦0.9，0.05≦y≦0.2，0.05≦z≦0.2，0.00001≦i<0.1，x+y+z+i＝1，所述M为Zr、Nb、Al、F、Mn、La中的至少一种。
在一些实施例中，所述掺杂型高镍三元材料的在0.2C的电流下首次可逆容量达到181-193mAh/g。
一种锂电池，包括所述的掺杂型高镍三元材料。
本公开实施例的优点：
(1)本公开实施例在制备掺杂型高镍三元前驱体时加入了过硫酸钠，过硫酸钠具有强氧化性，可以提高高镍三元前驱体中镍的平均价态，缓解阳离子混排造成的容量衰减问题。
(2)本公开实施例在制备掺杂型高镍三元前驱体时采用了二次烧结，先采用低温预烧，之后高温烧结，该法可以有效的降低材料的表面碱含量，增大材料的导电性，减少电池的极化，从而提高材料的导电性及循环寿命。
(3)本公开实施例在制备掺杂型高镍三元前驱体时加入了掺杂元素，掺杂元素的加入可以有效的提高高镍三元材料的热稳定性，进而提高材料的安全性能及循环寿命。
(4)本公开实施例所制备的高镍三元材料是用经过硫酸钠(氧化剂)及二次烧结的掺杂型高镍三元前驱体制备，通过这种方法制备的掺杂型高镍三元材料表现除了高的比容量和长的循环寿命，此外，在高温下依然表现出了高的比容量和长的循环寿命。
附图说明
图1为本公开的实施例1及对比例1制备的材料在0.2C的电流密度下的循环性能图；
图2为本公开的实施例1制备的掺杂型高镍三元材料的SEM图。
具体实施方式
为了对本公开进行深入的理解，下面结合实例对本公开若干实验方案进行描述，以进一步的说明本公开的特点和优点，任何不偏离本公开主旨的变化或者改变能够为本领域的技术人员理解，本公开的保护范围由所属权利要求范围确定。
本公开实施例中未注明具体条件者，按照常规条件或者制造商建议的条件进行。所用未注明生产厂商者的原料、试剂等，均为可以通过市售购买获得的常规产品。
实施例1
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液及浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到溶液C；
(3)将溶液C置于140℃烘箱中保温6h，得到气凝胶D；
(4)将气凝胶D充分研磨，在氧气氛围中200℃保温2h，之后升温至500℃保温6h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源充分研磨混合，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1(锂源中锂离子的量为0.2-0.25mol)，在氧气气氛中750℃保温12h，退火后，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到193mAh/g。
首次充放电过程中部分活性锂参与构建SEI膜，而无法脱出重回正极；首次脱锂过程发生不可逆相变；首次脱锂后，材料动力学特性降低。
上述所制备的掺杂型高镍三元材料作为锂离子电池正极材料表现出了优异的电化学性能，在0.2C的电流下首次可逆容量达到193mAh/g，经过300次充放电循环后可逆容量仍有180mAh/g，在5C的电流下经过200次充放电循环后可逆容量仍有161mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量仍然有173mAh/g。
实施例2
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶液溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.05mol/L的过硫酸钠溶液及浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于140℃烘箱中保温6h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中200℃保温3h，之后升温至500℃保温6h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源充分研磨混合，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中750℃保温12h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到184mAh/g。
上述所制备的掺杂型高镍三元材料作为锂离子电池正极材料表现出了优异的电化学性能，在0.2C的电流下经过300次充放电循环后可逆容量仍有166mAh/g，在5C的电流下经过200次充放电循环后可逆容量仍有146mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量仍然有163mAh/g。
实施例3
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.15mol/L的过硫酸钠溶液及浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于140℃烘箱中保温6h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中200℃保温2h，升温至500℃保温8h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源混合研磨，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中750℃保温12h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到186mAh/g。
上述所制备的掺杂型高镍三元材料作为锂离子电池正极材料表现出了优异的电化学性能，在0.2C的电流下经过300次充放电循环后可逆容量仍有170mAh/g，在5C的电流下经过200次充放电循环后可逆容量仍有128mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量仍然有158mAh/g。
实施例4
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液及浓度均为0.05mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于140℃烘箱中保温6h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中200℃保温2h，升温至500℃保温4h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源混合研磨，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中750℃保温12h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.799Co 0.1Mn 0.1NbLa 0.001O 2，在0.2C的电流下首次可逆容量达到183mAh/g。
上述所制备的掺杂型高镍三元材料作为锂离子电池正极材料表现出了优异的电化学性能，在0.2C的电流下经过300次充放电循环后可逆容量仍有165mAh/g，在5C的电流下经过200次充放电循环后可逆容量仍有133mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量仍然有133mAh/g。
实施例5
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液及浓度均为0.005mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于140℃烘箱中保温6h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中250℃保温2h，升温至500℃保温6h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源混合研磨，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中700℃保温12h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.7999Co 0.1Mn 0.1NbLa 0.0001O 2，在0.2C的电流下首次可逆容量达到181mAh/g。
上述所制备的掺杂型高镍三元材料作为锂离子电池正极材料表现出了优异的电化学性能，在0.2C的电流下经过300次充放电循环后可逆容量仍有164mAh/g，在5C的电流下经过200次充放电循环后可逆容量仍有139mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量仍然有142mAh/g。
实施例6
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液及浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于120℃烘箱中保温4h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中150℃保温2h，升温至400℃保温6h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源混合研磨，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中600℃保温8h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到182mAh/g。
上述所制备的高镍三元材料作为锂离子电池正极材料，在0.2C的电流下经过300次充放电循环后可逆容量有159mAh/g，在5C的电流下经过200次充放电循环后可逆容量有135mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量有123mAh/g。
实施例7
一种掺杂型高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液及浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中混合并充分搅拌，得到混合溶液B；
(2)向溶液B中加入100mL氨水溶液，并加入10mL硝酸，混匀后得到混合溶液C；
(3)将溶液C置于180℃烘箱中保温8h，得到气凝胶D；
(4)将气凝胶D进行研磨，在氧气氛围中250℃保温3h，升温至600℃保温8h，即得到掺杂型高镍三元前驱体；
(5)将掺杂型高镍三元前驱体与锂源混合研磨，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中900℃保温16h，退火，研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到187mAh/g。
上述所制备的高镍三元材料作为锂离子电池正极材料，在0.2C的电流下经过300次充放电循环后可逆容量有168mAh/g，在5C的电流下经过200次充放电循环后可逆容量有135mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过200次充放电循环后可逆容量有133mAh/g。
对比例1(不掺杂元素)
一种高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度为0.1mol/L的过硫酸钠溶液与100mL氨水溶液与A混合并充分搅拌，得到混合溶液B；
(2)将溶液B置于140℃烘箱中保温6h得到气凝胶C；
(3)将气凝胶C充分研磨，在氧气氛围中500℃保温6h，即得到高镍三元前驱体；
(4)将高镍三元前驱体与锂源充分研磨混合，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中700℃保温12h，退火后充分研磨并过325目筛，即得到高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.8Co 0.1Mn 0.1O 2，在0.2C的电流下首次可逆容量达到162mAh/g。
对比例1所制备的高镍三元材料作为锂离子电池正极材料，在0.2C的电流下经过100次充放电循环后可逆容量有83mAh/g，在5C的电流下经过100次充放电循环后可逆容量有60mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过100次充放电循环后可逆容量仍然有68mAh/g。
对比例2(不采用丙烯酸合成)
一种高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A，配制浓度均为0.015mol/L的硝酸镧及磷酸氧铌溶液，加入溶液A中充分混合，得到溶液B；
(2)将溶液B置于140℃烘箱中保温6h得到气凝胶C；
(3)将气凝胶C充分研磨，在氧气氛围中500℃保温6h，即得到掺杂型高镍三元前驱体；
(4)将掺杂型高镍三元前驱体与锂源充分研磨混合，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中700℃保温12h，退火后充分研磨并过325目筛，即得到掺杂型高镍三元材料。
一种掺杂型高镍三元材料，其化学式为LiNi 0.797Co 0.1Mn 0.1NbLa 0.003O 2，在0.2C的电流下首次可逆容量达到158mAh/g。
对比例2所制备的高镍三元材料作为锂离子电池正极材料，在0.2C的电流下经过100次充放电循环后可逆容量有95mAh/g，在5C的电流下经过100次充放电循环后可逆容量有63mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过100次充放电循环后可逆容量仍然有78mAh/g。
对比例3(不掺杂元素和不采用丙烯酸合成)
一种高镍三元材料的制备方法，包括以下步骤：
(1)配制摩尔比为Ni：Co：Mn＝0.8：0.1：0.1且总浓度为1mol/L的可溶性硝酸镍、可溶性硝酸钴以及可溶性醋酸锰，溶解于200mL去离子水中，搅拌至完全溶解得到溶液A；
(2)将溶液A置于140℃烘箱中保温6h得到气凝胶B；
(3)将气凝胶B充分研磨，在氧气氛围中200℃保温2h后升温至500℃保温6h即得到高镍三元前驱体；
(4)将高镍三元前驱体与锂源充分研磨混合，锂源中锂的含量与步骤(1)制备的溶液A中金属离子总含量的化学计量比为1.06：1，在氧气气氛中700℃保温12h，退火后充分研磨并过325目筛，即得到高镍三元材料。一种掺杂型高镍三元材料，其化学式为LiNi 0.8Co 0.1Mn 0.1O 2，在0.2C的电流下首次可逆容量达到152mAh/g。
对比例3制备的高镍三元材料作为锂离子电池正极材料，在0.2C的电流下经过100次充放电循环后可逆容量有89mAh/g，在5C的电流下经过100次充放电循环后可逆容量有69mAh/g。在70℃环境下对电池进行循环性能测试，在0.1C的电流下经过100次充放电循环后可逆容量仍然有73mAh/g。
将实施例及对比例制备材料的制备条件及测试结果对比，得到表1的所示结果。
表1实施例1-7及对比例1-3所制备材料的循环性能对比
Figure PCTCN2021123411-appb-000001
由表1及图1可以看出，采用氧化剂及二次烧结辅助元素掺杂的方法可以有效提高材料的电化学性能，用此法制备出的材料表现出高的比容量及长且稳定的循环性能。从图2可以看出，通过该法制备的材料颗粒均一、形状为规则的球状。
以上对本公开实施例提供的一种掺杂型高镍三元材料及其制备方法进行了详细的介绍，本文中应用了具体实施例对本公开的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本公开的方法及其核心思想，包括若干实施方式，并且也使得本领域的任何技术人员都能够实践本公开，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本公开原理的前提下，还可以对本公开进行若干改进和修饰，这些改进和修饰也落入本公开权利要求的保护范围内。本公开专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种掺杂型高镍三元材料的制备方法，包括以下步骤：
    (1)将镍源、钴源、锰源溶于溶剂中，混合得到溶液A，再加入氧化剂和掺杂元素，搅拌，得到溶液B；
    (2)将络合剂、硝酸加入溶液B，搅拌，得到溶液C；
    (3)将溶液C烘干，研磨，得到气凝胶D；
    (4)将气凝胶D进行第一次烧结，再继续第二次烧结，得到前驱体粉末E；
    (5)将前驱体粉末E与锂源混合，煅烧，研磨，过筛即得掺杂型高镍三元材料；所述掺杂元素为Zr、Nb、Al、F、Mn、La中的至少一种。
  2. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述镍源、钴源、锰源为六水合硝酸镍、六水合硝酸钴、四水合醋酸锰；所述镍源、钴源、锰源的摩尔比为(0.6-0.9)：(0.05-0.2)：(0.05-0.2)。
  3. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述氧化剂为过硫酸钠、过氧化钠或过硫酸铵中的至少一种。
  4. 根据权利要求1所述的制备方法，其中，步骤(1)中，所述掺杂元素是配置成硝酸盐、磷酸盐或硫酸盐的形式添加到溶液A中。
  5. 根据权利要求1所述的制备方法，其中，步骤(2)中，所述络合剂为丙烯酸溶液。
  6. 根据权利要求1所述的制备方法，其中，步骤(4)中，所述第一次烧结的温度为150℃-250℃，第一次烧结的时间为1-3h，气氛为空气或氧气；所述第二次烧结的温度为400℃-600℃，第二次烧结的时间为4-8h，气氛为空气或氧气。
  7. 根据权利要求1所述的制备方法，其中，步骤(5)中，所述锂源为碳酸锂或氢氧化锂。
  8. 一种掺杂型高镍三元材料，其中，所述掺杂型高镍三元材料是由权利要求1-7任一项所述的制备方法制得，所述掺杂型高镍三元材料的化学式为LiNi xCo yMn zM iO 2，所述M为Zr、Nb、Al、F、Mn、La中的至少一种；其中0.6≦x≦0.9，0.05≦y≦0.2，0.05≦z≦0.2，0.00001≦i<0.1，x+y+z+i＝1。
  9. 根据权利要求8所述的掺杂型高镍三元材料，其中，所述掺杂型高镍三元材料的首次可逆容量为181-193mAh/g。
  10. 一种锂电池，包括权利要求8-9任一项所述的掺杂型高镍三元材料。
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