CN114477318A - High-aspect-ratio ternary positive electrode material, and preparation method and application thereof - Google Patents

High-aspect-ratio ternary positive electrode material, and preparation method and application thereof Download PDF

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CN114477318A
CN114477318A CN202210392363.9A CN202210392363A CN114477318A CN 114477318 A CN114477318 A CN 114477318A CN 202210392363 A CN202210392363 A CN 202210392363A CN 114477318 A CN114477318 A CN 114477318A
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nickel
cobalt
manganese
precursor mixture
lithium
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李成
范未峰
张彬
张萍
侯世林
郝长旺
罗涵钰
王政强
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Yibin Libao New Materials Co Ltd
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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
    • 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
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    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • 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

Abstract

The invention discloses a ternary cathode material with a high aspect ratio, a preparation method and application thereof, and relates to the technical field of lithium ion batteries. The preparation method of the ternary cathode material with the high aspect ratio comprises the steps of mixing a nickel-cobalt-manganese precursor with a lithium source, an antimony-containing compound, a niobium-containing compound and a molybdenum-containing compound to obtain a precursor mixture, and sintering the precursor mixture in an oxygen-containing atmosphere to obtain the ternary cathode material. The ternary cathode material prepared by the preparation method provided by the invention has a high aspect ratio hierarchical three-dimensional material, and the cycle performance is remarkably improved.

Description

High-aspect-ratio ternary positive electrode material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a ternary cathode material with a high aspect ratio, and a preparation method and application thereof.
Background
Currently, the micro-sphere of ternary cathode materials is formed by close packing of many randomly oriented primary nanoparticles, in which Li is present+Migration must occur across grain boundaries, particularly between grains with non-uniform crystallographic planes, so the randomly oriented primary nanoparticles in the ternary cathode material extend Li+The diffusion pathway. During charging and discharging of the material, Li+And (3) de-intercalation, phase change is continuously found, and further the anisotropic change of the lattice parameter is realized, and the change is more obvious in the nickel-rich ternary cathode material. In addition, in the charge and discharge process of the nickel-rich ternary cathode material, a large amount of anisotropic lattices expand/contract, and due to asynchronous volume change of different lattices, severe micro strain is generated at the boundary of randomly oriented main particles, so that cracks can develop and propagate along the crystal boundary until secondary particles are completely crushed, and even primary particles fall off, which is considered as one of main reasons for the rapid reduction of the capacity retention rate of the nickel-rich NCM material in long-term circulation.
Li in view of hexagonal NCM material+High anisotropy of diffusion and lattice expansion/contraction, morphological modulation would be an effective method of cyclic stability. The radially oriented high aspect ratio single crystal host particles penetrate from the surface to the center, Li+Ions diffuse directly from the center to the surface without crossing the grain boundaries, thus creating convenient three-dimensional Li + channels. In addition, the radial primary particles with consistent crystal orientation can remarkably reduce volume-induced intercrystalline stress through synergistic expansion and contraction, thereby inhibiting pulverization of secondary particles and promoting cycle stability.
Therefore, if the NCM material with a high aspect ratio can be prepared, it is advantageous to further improve the performance of the material.
Disclosure of Invention
The invention aims to provide a high-aspect-ratio ternary cathode material and a preparation method thereof, and aims to prepare a high-aspect-ratio cathode material so as to improve the performance of the material.
The invention also aims to provide application of the ternary cathode material with the high aspect ratio in preparation of a lithium ion battery.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing a high aspect ratio ternary cathode material, comprising: mixing a nickel-cobalt-manganese precursor with a lithium source, an antimony-containing compound, a niobium-containing compound and a molybdenum-containing compound to obtain a precursor mixture, and sintering the precursor mixture in an oxygen-containing atmosphere.
In an alternative embodiment, a nickel-cobalt-manganese precursor is mixed with a lithium source to obtain a first precursor mixture;
mixing a nickel-cobalt-manganese precursor, a lithium source and an antimony-containing compound to obtain a second precursor mixture;
mixing a nickel-cobalt-manganese precursor, a lithium source and a niobium-containing compound to obtain a third precursor mixture;
mixing a nickel-cobalt-manganese precursor, a lithium source and a molybdenum-containing compound to obtain a fourth precursor mixture;
mixing the first precursor mixture, the second precursor mixture, the third precursor mixture and the fourth precursor mixture, and sintering in an oxygen-containing atmosphere;
preferably, the chemical formula of the nickel-cobalt-manganese precursor is NixCoyMn1−x−y (OH)2，x≥0.8；
Controlling the molar ratio of lithium to nickel, cobalt and manganese to be 1.02-1.07:1 in the preparation process of the first precursor mixture;
in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.02-1.07:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.3-0.7%;
in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.02-1.07:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.5-1.5%;
in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and molybdenum is controlled to be 1.02-1.07:1, and the proportion of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum is controlled to be 0.5-1.0%;
preferably, the mass ratio of the first precursor mixture, the second precursor mixture, the third precursor mixture and the fourth precursor mixture is 1:0.8-1.2:0.8-1.2: 0.8-1.2.
In an alternative embodiment, the molar ratio of lithium to nickel cobalt manganese is controlled to be 1.04-1.06:1 during the preparation of the first precursor mixture;
in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.04-1.06:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.4-0.6%;
in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.04-1.06:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.8-1.2%;
in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel-cobalt-manganese-molybdenum is controlled to be 1.04-1.06:1, and the ratio of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum is controlled to be 0.7-0.8%.
In alternative embodiments, the antimony-containing compound, the niobium-containing compound, and the molybdenum-containing compound are all oxides;
more preferably, the antimony-containing compound is Sb2O3The niobium-containing compound is Nb2O5The molybdenum-containing compound is Mo2O3；
Preferably, the lithium source is at least one of lithium hydroxide, lithium nitrate, lithium sulfate and lithium chloride.
In an optional embodiment, the sintering temperature is 720-820 ℃, and the sintering time is 8-15 h;
preferably, the sintering temperature is 750-800 ℃, and the sintering time is 8-12 h.
In an alternative embodiment, the nickel-cobalt-manganese precursor has a spheroidal morphology with a diameter of 8-12 μm.
In an alternative embodiment, the method for preparing the nickel-cobalt-manganese precursor comprises: dissolving nickel salt, cobalt salt and manganese salt, mixing and reacting with continuously injected sodium hydroxide solution and ammonia water solution in a reactor, and filtering, washing and drying after the reaction is finished;
preferably, the concentration of the sodium hydroxide solution is 2 mol/L, and the pH value of the reaction system is controlled to be 10-11 by regulating the adding rate of the sodium hydroxide solution.
In an alternative embodiment, the concentration of the aqueous ammonia solution is 0.6 to 1.0mol/L, and the linear velocity of the edge of the stirring impeller is controlled to 6.0 to 6.5m/s during the reaction.
In a second aspect, the present invention provides a high aspect ratio ternary positive electrode material prepared by the preparation method of any one of the preceding embodiments;
preferably, in the high aspect ratio ternary positive electrode material, the length-to-width ratio of the single crystal is greater than or equal to 10.
In a third aspect, the present invention provides a use of the high aspect ratio ternary cathode material of the previous embodiments in the preparation of a lithium ion battery.
The invention has the following beneficial effects: the preparation method comprises the steps of mixing a nickel-cobalt-manganese precursor with a lithium source, an antimony-containing compound, a niobium-containing compound and a molybdenum-containing compound to obtain a precursor mixture, and sintering the precursor mixture in an oxygen-containing atmosphere to obtain the ternary cathode material. The ternary cathode material prepared by the preparation method provided by the invention has a high aspect ratio hierarchical three-dimensional material, and the performance is remarkably improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a topographical view of a positive electrode material prepared in example 1; FIGS. 1 (a) and (b) show test charts at different magnifications;
FIG. 2 is a morphology chart of the cathode material prepared in example 2 and example 3; fig. 2 (a) is a topographic map of the cathode material obtained in example 2, and (b) is a topographic map of the cathode material obtained in example 3;
FIG. 3 is a morphology chart of the positive electrode material prepared in the comparative example; FIG. 3 (a) is a morphology diagram of the product obtained in comparative example 1; (b) and (f) are the morphology graphs of the products obtained in comparative example 2 to comparative example 6 respectively.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment of the invention provides a preparation method of a ternary cathode material with a high aspect ratio, which comprises the following steps:
s1 preparation of precursor
The preparation method of the nickel-cobalt-manganese precursor comprises the following steps: dissolving nickel salt, cobalt salt and manganese salt, mixing the dissolved nickel salt, cobalt salt and manganese salt with continuously injected sodium hydroxide solution and ammonia water solution in a reactor for reaction, and filtering, washing and drying after the reaction is finished. In the reaction process, ammonia water plays a role of a complexing agent, sodium hydroxide is used for adjusting the pH value to 10-11, nickel-cobalt-manganese hydroxide is obtained through reaction, and the reaction is complete when no precipitate is generated.
Specifically, the nickel salt, cobalt salt and manganese salt may be general nitrate, sulfate, etc., and are not limited thereto. The proportion of nickel, cobalt and manganese can be adjusted according to the conventional proportion, and the chemical formula of the nickel, cobalt and manganese precursor is approximately controlled to be NixCoyMn1−x−y (OH)2，x≥0.8。
In some embodiments, the concentration of the sodium hydroxide solution is 2 mol/L, and the pH value of the reaction system is controlled to be 10-11 by regulating the adding rate of the sodium hydroxide solution; the concentration of the ammonia water solution is 0.6-1.0mol/L, and the linear velocity of the edge of the stirring impeller is controlled to be 6.0-6.5m/s in the reaction process. The prepared nickel-cobalt-manganese precursor is in a sphere-like shape by further controlling the concentration of ammonia water and the stirring speed.
Specifically, the ammonia water concentration may be 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1.0mol/L, or the like, or may be any value between the above adjacent concentration values; the linear velocity of the edge of the stirring impeller is controlled to be 6.0m/s, 6.1m/s, 6.2m/s, 6.3m/s, 6.4m/s, 6.5m/s, etc. in the reaction process, and can be any value between the above adjacent linear velocities.
S2, sintering to prepare the ternary cathode material
Mixing a nickel-cobalt-manganese precursor with a lithium source to obtain a first precursor mixture NCM; mixing a nickel-cobalt-manganese precursor, a lithium source and an antimony-containing compound to obtain a second precursor mixture Sb-NCM; mixing a nickel-cobalt-manganese precursor, a lithium source and a niobium-containing compound to obtain a third precursor mixture Nb-NCM; mixing a nickel-cobalt-manganese precursor, a lithium source and a molybdenum-containing compound to obtain a fourth precursor mixture Mo-NCM; and mixing the first precursor mixture, the second precursor mixture, the third precursor mixture and the fourth precursor mixture, and sintering in an oxygen-containing atmosphere.
The inventors carried out mixed sintering using NCM, Sb-NCM, Nb-NCM and Mo-NCM to fix the grain boundaries to reduce interdiffusion and to minimize coarsening. Li, prepared by penetrating single crystal host particles with high aspect ratio in radial orientation from surface to center+Ions diffuse directly from the center to the surface without crossing the grain boundaries, thus creating convenient three-dimensional Li+A channel.
In other embodiments, the nickel-cobalt-manganese precursor can be directly mixed with a lithium source, an antimony-containing compound, a niobium-containing compound, and a molybdenum-containing compound to obtain a precursor mixture, and the precursor mixture can be sintered in an oxygen-containing atmosphere.
In some embodiments, the molar ratio of lithium to nickel cobalt manganese is controlled to be 1.02 to 1.07:1 during the preparation of the first precursor mixture; in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.02-1.07:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.3-0.7%; in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.02-1.07:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.5-1.5%; in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel-cobalt-manganese-molybdenum is controlled to be 1.02-1.07:1, and the ratio of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum is controlled to be 0.5-1.0%. By further controlling the doping ratio of antimony, niobium and molybdenum, the material with a higher aspect ratio can be obtained, and the performance of the material can be improved.
Specifically, the molar ratio of lithium to nickel, cobalt, and manganese in the first precursor mixture is 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, and so forth.
Specifically, in the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, and the like; the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony can be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, etc.
Specifically, in the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese, niobium is 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, etc.; the percentage of niobium in the total molar amount of nickel, cobalt, manganese, and niobium may be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, etc.
Specifically, in the fourth precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and molybdenum is 1.02:1, 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, etc.; the proportion of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% and the like.
Further, the mass ratio of the first precursor mixture to the second precursor mixture to the third precursor mixture to the fourth precursor mixture is 1:0.8-1.2:0.8-1.2: 0.8-1.2. The amount of the four precursor mixtures can be about equal, and can be 1:0.8:0.8:0.8, 1:0.9:0.9:0.9, 1:1.0:1.0:1.0, 1:1.1:1.1:1.1, 1:1.2:1.2:1.2, and the like. The amounts of the second, third and fourth precursor mixtures may or may not be equal.
In a preferred embodiment, the molar ratio of lithium to nickel cobalt manganese is controlled to be 1.04-1.06:1 during the preparation of the first precursor mixture; in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.04-1.06:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.4-0.6%; in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.04-1.06:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.8-1.2%; in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel-cobalt-manganese-molybdenum is controlled to be 1.04-1.06:1, and the ratio of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum is controlled to be 0.7-0.8%. By further controlling the doping ratio of antimony, niobium and molybdenum, the cathode material with better cycle performance is obtained.
In some embodiments, the antimony-containing compound, the niobium-containing compound, and the molybdenum-containing compound are all oxides; preferably, the antimony-containing compound is Sb2O3The niobium-containing compound is Nb2O5The molybdenum-containing compound is Mo2O3(ii) a Minimizing coarsening is achieved by introducing higher valence ions to mitigate interdiffusion by fixing the particle boundaries.
In some embodiments, the lithium source is at least one of lithium hydroxide, lithium nitrate, lithium sulfate, and lithium chloride, typically LiOH ∙ H2O。
Further, the sintering temperature is 720-820 ℃, and the sintering time is 8-15 h; preferably, the sintering temperature is 750-800 ℃, and the sintering time is 8-12 h. And the electrical property of the ternary cathode material is ensured by controlling the sintering temperature and time, so that a structure with a high aspect ratio is obtained.
Specifically, the sintering temperature can be 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃, 810 ℃, 820 ℃ and the like, and the sintering time can be 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and the like.
The embodiment of the invention provides a high aspect ratio ternary cathode material, which is prepared by the preparation method, wherein the cathode material is a graded high aspect ratio ternary cathode material, and the graded material is a three-dimensional material formed by self-assembly of a low-dimensional material (one-dimensional or two-dimensional); the length-width ratio (L/W) of the low-dimensional material with the high aspect ratio is more than or equal to 10.
In some embodiments, the high aspect ratio ternary cathode materials can be prepared to form lithium ion batteries, giving the battery materials excellent cycling stability performance.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a ternary cathode material with a high aspect ratio, which comprises the following steps:
(1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water, and adding the mixed metal salt aqueous solution into N2Pumped into a continuous stirred tank reactor under conditions. Simultaneously, 2 mol L of-1And 0.8mol L of sodium hydroxide solution-1NH of (2)3•H2And respectively injecting the O solution into the reactors, wherein the linear velocity of the outer edge of a stirring impeller in the stirring tank reactor is 6.3m/s, and the pH value of the system is controlled to be 11 by adjusting the adding rate of the sodium hydroxide solution. After the reaction was completed, a precursor powder was obtained by filtration, washing and vacuum drying. By controlling the molar ratio of the nickel, cobalt and manganese raw materials, the chemical formula of the high-nickel precursor is Ni0.8Co0.1Mn0.1(OH)2。
Through detection: the grading appearance of the precursor is similar to a sphere.
(2) Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2And O, mixing according to the molar ratio of the lithium to the nickel, cobalt and manganese of 1.05:1 to obtain a first precursor mixture NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Sb2O3And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-antimony to be 1.05:1, and controlling the proportion of antimony in the total molar amount of nickel-cobalt-manganese-antimony to be 0.5%, so as to obtain a second precursor mixture Sb-NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Nb2O5And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-niobium to be 1.05:1, and controlling the ratio of niobium to the total molar amount of nickel-cobalt-manganese-niobium to be 1.0%, so as to obtain a third precursor mixture Nb-NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Mo2O3And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-molybdenum to be 1.05:1, and controlling the proportion of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum to be 0.75%, so as to obtain a fourth precursor mixture Mo-NCM.
Mixing NCM, Sb-NCM, Nb-NCM and Mo-NCM according to the mass ratio of 1:1:1:1, sintering in an atmosphere with the oxygen content of more than 95%, controlling the sintering temperature at 770 ℃ and the sintering time at 10h to obtain the ternary cathode material with the high aspect ratio.
Example 2
The embodiment provides a preparation method of a ternary cathode material with a high aspect ratio, which comprises the following steps:
(1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water, and adding the mixed metal salt aqueous solution into N2Pumped into a continuous stirred tank reactor under conditions. Simultaneously, 2 mol L of-1And 0.6moL L of sodium hydroxide solution-1NH of3•H2The O solution is respectively injected into the reactors, the linear velocity of the outer edge of the stirring impeller in the stirring tank reactor is 6.0m/s, and the pH value of the system is controlled to be 10 by adjusting the adding rate of the sodium hydroxide solution. After the reaction was completed, a precursor powder was obtained by filtration, washing and vacuum drying. By controlling the molar ratio of the nickel, cobalt and manganese raw materials, the chemical formula of the high-nickel precursor is Ni0.9Co0.07Mn0.03(OH)2。
Through detection: the grading appearance of the precursor is similar to a sphere.
(2) Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2And O, mixing according to the molar ratio of the lithium to the nickel, cobalt and manganese of 1.02:1 to obtain a first precursor mixture NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Sb2O3And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-antimony to be 1.02:1, and controlling the proportion of antimony in the total molar amount of nickel-cobalt-manganese-antimony to be 0.3%, so as to obtain a second precursor mixture Sb-NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Nb2O5Mixing, controlling the molar ratio of lithium to nickel, cobalt, manganese and niobium to be 1.02:1 and controllingThe proportion of the prepared niobium in the total molar weight of nickel, cobalt, manganese and niobium is 0.5 percent, and a third precursor mixture Nb-NCM is obtained.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Mo2O3And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-molybdenum to be 1.02:1, and controlling the proportion of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum to be 0.5%, so as to obtain a fourth precursor mixture Mo-NCM.
Mixing NCM, Sb-NCM, Nb-NCM and Mo-NCM according to the mass ratio of 1:0.8:0.8:0.8, sintering in an atmosphere with the oxygen content of more than 95%, controlling the sintering temperature to be 720 ℃ and the sintering time to be 15h, and obtaining the ternary cathode material with the high aspect ratio in a graded manner.
Example 3
The embodiment provides a preparation method of a ternary cathode material with a high aspect ratio, which comprises the following steps:
(1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in deionized water, and adding the mixed metal salt aqueous solution into N2Pumped into a continuous stirred tank reactor under conditions. Simultaneously, 2 mol L of-1And 1.0moL L of sodium hydroxide solution-1NH of (2)3•H2And respectively injecting the O solution into the reactors, wherein the linear velocity of the outer edge of a stirring impeller in the stirring tank reactor is 6.5m/s, and the pH value of the system is controlled to be 11 by adjusting the adding rate of the sodium hydroxide solution. After the reaction was completed, a precursor powder was obtained by filtration, washing and vacuum drying. By controlling the molar ratio of the nickel, cobalt and manganese raw materials, the chemical formula of the high-nickel precursor is Ni0.8Co0.1Mn0.1(OH)2。
And (3) detection: the grading appearance of the precursor is similar to a sphere.
(2) Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2And O, mixing according to the molar ratio of the lithium to the nickel, cobalt and manganese of 1.07:1 to obtain a first precursor mixture NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Sb2O3Mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-antimony to be 1.07:1, and controlling the proportion of antimony in the total molar amount of nickel-cobalt-manganese-antimony to be 0.7%, thereby obtaining the lithium-nickel-manganese-antimony alloyTo the second precursor mixture Sb-NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Nb2O5And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-niobium to be 1.07:1, and controlling the proportion of niobium in the total molar amount of nickel-cobalt-manganese-niobium to be 1.5%, so as to obtain a third precursor mixture Nb-NCM.
Mixing the precursor powder obtained in the step (1) with LiOH ∙ H2O and Mo2O3And mixing, controlling the molar ratio of lithium to nickel-cobalt-manganese-molybdenum to be 1.07:1, and controlling the proportion of molybdenum in the total molar amount of nickel-cobalt-manganese-molybdenum to be 1.0%, so as to obtain a fourth precursor mixture Mo-NCM.
Mixing NCM, Sb-NCM, Nb-NCM and Mo-NCM according to the mass ratio of 1:1.2:1.2:1.2, sintering in an atmosphere with the oxygen content of more than 95%, controlling the sintering temperature at 820 ℃ and the sintering time at 8h, and obtaining the ternary cathode material with the high aspect ratio in a graded manner.
Comparative example 1
The only difference from example 1 is: Sb-NCM is not introduced during sintering, and NCM, Nb-NCM and Mo-NCM are mixed in equal proportion.
Comparative example 2
The only difference from example 1 is: Nb-NCM is not introduced during sintering, and only NCM, Sb-NCM and Mo-NCM are mixed in equal proportion.
Comparative example 3
The only difference from example 1 is: Mo-NCM is not introduced during sintering, and only NCM, Sb-NCM and Nb-NCM are mixed in equal proportion.
Comparative example 4
The only difference from example 1 is: sb2O3Substitution to Al2O3。
Comparative example 5
The only difference from example 1 is: the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is 1.0%, the proportion of niobium in the total molar amount of nickel, cobalt, manganese and niobium is 2.0%, and the proportion of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum is 1.0%.
Comparative example 6
The only difference from example 1 is: the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is 0.2%, the proportion of niobium in the total molar amount of nickel, cobalt, manganese and niobium is 0.3%, and the proportion of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum is 0.3%.
Test example 1
The topography of the cathode material obtained in test example 1 is shown in fig. 1.
As can be seen from fig. 1, the cathode material prepared in example 1 is spheroidal, which is formed by self-assembly from low-dimensional rods. The low dimensional rods are approximately 2.371 μm in length and 158 nm in width, with significant high aspect ratio features.
Test example 2
The morphology maps of the cathode materials obtained in test examples 2 and 3 are shown in fig. 2.
Fig. 2 (a) is a topographic map of the positive electrode material obtained in example 2, and (b) is a topographic map of the positive electrode material obtained in example 3.
Test example 3
The morphology graphs of the positive electrode materials obtained in comparative examples 1 to 6 were tested, and the results are shown in fig. 3, in which (a) in fig. 3 is the morphology graph of the product obtained in comparative example 1; (b) and (f) are the morphology graphs of the products obtained in comparative example 2 to comparative example 6 respectively.
As can be seen from FIG. 3, the aspect ratio of the cathode material obtained in the comparative example is smaller than that of examples 1-3, and compared with the examples in the comparative examples 1-3, the three high-valence elements Sb, Nb and Mo have a synergistic effect on the high aspect ratio morphology of the cathode material, and the three elements jointly promote the longitudinal growth of the low-dimensional rod. Comparative example 4 compared to the examples, shows that different elements have different effects on the growth of low dimensional rods. Compared with the examples, the comparative examples 5 to 6 show that the doping amount of Sb, Nb and Mo needs to be controlled within a certain range, the doping amount is too low, the needle punching effect on the low-dimensional rods is weakened, and the degree of transverse growth is enhanced. The doping amount is too high, the low-dimensional rod can be influenced by doping elements in the longitudinal production process, the phenomenon of discontinuous growth occurs, and the longitudinal size is further reduced compared with the embodiment.
The aspect ratios and the electrical properties of the products obtained in examples 1 to 3 and comparative examples 1 to 6 were tested, and the results are shown in table 1.
And (3) testing electrical properties: at 1.0C (200 mA/g) constantUnder constant current, testing at 25 deg.C within 3.0-4.2V voltage range, and recording the first discharge capacity C1And recording the discharge capacity C of the ring after 100 cycles100Finally, the capacity retention rate eta is calculated (the calculation mode is eta = C)100/C1*100%）。
TABLE 1 results of performance test of products obtained in examples and comparative examples
Figure P_220414135203088_088370001
As can be seen from table 1, the cathode material prepared in the examples of the present application has a high aspect ratio, a high capacity retention rate, and excellent cycle stability.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a ternary cathode material with a high aspect ratio is characterized by comprising the following steps:
mixing a nickel-cobalt-manganese precursor with a lithium source, an antimony-containing compound, a niobium-containing compound and a molybdenum-containing compound to obtain a precursor mixture, and sintering the precursor mixture in an oxygen-containing atmosphere.
2. The method of claim 1, wherein the nickel-cobalt-manganese precursor is mixed with a lithium source to obtain a first precursor mixture;
mixing the nickel-cobalt-manganese precursor, a lithium source and an antimony-containing compound to obtain a second precursor mixture;
mixing the nickel-cobalt-manganese precursor, a lithium source and a niobium-containing compound to obtain a third precursor mixture;
mixing the nickel-cobalt-manganese precursor, a lithium source and a molybdenum-containing compound to obtain a fourth precursor mixture;
mixing the first precursor mixture, the second precursor mixture, the third precursor mixture and the fourth precursor mixture, and sintering in an oxygen-containing atmosphere;
the chemical formula of the nickel-cobalt-manganese precursor is NixCoyMn1−x−y(OH)2，x≥0.8；
Controlling the molar ratio of lithium to nickel, cobalt and manganese to be 1.02-1.07:1 in the preparation process of the first precursor mixture;
in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.02-1.07:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.3-0.7%;
in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.02-1.07:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.5-1.5%;
in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and molybdenum is controlled to be 1.02-1.07:1, and the proportion of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum is controlled to be 0.5-1.0%;
the mass ratio of the first precursor mixture to the second precursor mixture to the third precursor mixture to the fourth precursor mixture is 1:0.8-1.2:0.8-1.2: 0.8-1.2.
3. The method according to claim 2, wherein the molar ratio of lithium to nickel, cobalt and manganese is controlled to be 1.04-1.06:1 during the preparation of the first precursor mixture;
in the preparation process of the second precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and antimony is controlled to be 1.04-1.06:1, and the proportion of antimony in the total molar amount of nickel, cobalt, manganese and antimony is controlled to be 0.4-0.6%;
in the preparation process of the third precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and niobium is controlled to be 1.04-1.06:1, and the ratio of niobium in the total molar amount of nickel, cobalt, manganese and niobium is controlled to be 0.8-1.2%;
in the preparation process of the fourth precursor mixture, the molar ratio of lithium to nickel, cobalt, manganese and molybdenum is controlled to be 1.04-1.06:1, and the ratio of molybdenum in the total molar amount of nickel, cobalt, manganese and molybdenum is controlled to be 0.7-0.8%.
4. The method according to claim 2, wherein the antimony-containing compound is Sb2O3The niobium-containing compound is Nb2O5The molybdenum-containing compound is Mo2O3；
The lithium source is at least one of lithium hydroxide, lithium nitrate, lithium sulfate and lithium chloride.
5. The method as claimed in claim 2, wherein the sintering temperature is 720-820 ℃ and the sintering time is 8-15 h.
6. The preparation method according to claim 2, wherein the nickel-cobalt-manganese precursor has a spherical-like morphology with a diameter of 8-12 μm.
7. The method according to claim 6, wherein the method for preparing the nickel-cobalt-manganese precursor comprises: dissolving nickel salt, cobalt salt and manganese salt, mixing and reacting with continuously injected sodium hydroxide solution and ammonia water solution in a reactor, and filtering, washing and drying after the reaction is finished;
the concentration of the sodium hydroxide solution is 2 mol/L, and the pH value of the reaction system is controlled to be 10-11 by regulating the adding rate of the sodium hydroxide solution.
8. The process according to claim 7, wherein the concentration of the aqueous ammonia solution is 0.6 to 1.0mol/L, and the linear velocity of the stirring impeller edge is controlled to 6.0 to 6.5m/s during the reaction.
9. A high aspect ratio ternary positive electrode material, characterized in that it is prepared by the preparation method of any one of claims 1 to 8;
in the high aspect ratio ternary cathode material, the length-to-width ratio of a single crystal is greater than or equal to 10.
10. Use of the high aspect ratio ternary positive electrode material of claim 9 in the preparation of a lithium ion battery.
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