CN111653765A - Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material - Google Patents

Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material Download PDF

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CN111653765A
CN111653765A CN202010492445.1A CN202010492445A CN111653765A CN 111653765 A CN111653765 A CN 111653765A CN 202010492445 A CN202010492445 A CN 202010492445A CN 111653765 A CN111653765 A CN 111653765A
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niobium
source
lithium
nickel
cobalt
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常程康
刘雨鸥
何辉辉
刘三超
董键
章冬云
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Shanghai Institute of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/52—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Abstract

The invention discloses a preparation method of a niobium-doped nickel-cobalt lithium aluminate anode material, which is characterized in that a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are sequentially added into deionized water and uniformly mixed to form a suspension; grinding the suspension to obtain slurry; spray drying the slurry to obtain a precursor of the niobium-doped nickel-cobalt lithium aluminate lithium battery anode material; and (3) putting the precursor into a crucible, putting the crucible into a tube furnace, and calcining the precursor in an oxygen atmosphere to obtain the niobium-doped lithium battery anode material. The nickel-cobalt lithium aluminate lithium battery anode material is obtained by solid-phase sintering, and structural distortion and structural collapse of the material in the charge and discharge process can be inhibited by utilizing the strong chemical bond of the Nb-O bond. Thereby enhancing the capacity retention rate and rate capability of the material.

Description

Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material
Technical Field
The invention relates to a lithium battery anode material, in particular to a preparation method of a niobium-doped nickel cobalt lithium aluminate anode material, belonging to the technical field of lithium ion battery manufacture.
Background
In recent years, society and economy have rapidly developed, and environmental pollution gradually becomes a key factor restricting improvement of life quality of people. In order to improve the environmental quality, new energy sources such as solar energy, wind energy, hydrogen energy and the like are gradually developed. Lithium batteries have been in use to alleviate environmental stress and fossil fuel shortage problems. In the existing lithium ion battery system, the negative electrode material adopts graphite without lithium ions, so that the positive electrode material determines the total amount of lithium ions which can be desorbed and occluded in the whole lithium ion battery, thereby having a decisive influence on the energy density of the lithium ion battery. At present, the most commonly used lithium battery positive electrode materials are mainly ternary positive electrode materials, including lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate. In order to increase the energy density of the battery, a high Ni ternary material is currently generally used. The discharge specific capacity increases with an increase in the Ni content, but there are also the following problems: (1) the multiplying power performance is not good, the capacity is not high when the battery is charged and discharged under the condition of high multiplying power, and the attenuation is very serious; (2) the structural stability is to be improved, and in the long-circulating process, the structure collapse easily occurs, and the transformation from the lamellar structure to the spinel phase and finally to the rock-salt phase easily occurs, so that the material capacity loss is caused.
In order to solve the above problems, researchers mainly modify the material from two aspects of doping and cladding. For example, patent CN110350171A discloses a method for preparing a rubidium-doped high-nickel ternary material, in which rubidium is doped to lithium site, and the radius of the rubidium is larger than that of lithium, so that the stability of the layered structure can be improved, the interlayer spacing is increased, the deintercalation of lithium ions is facilitated, and the capacity retention rate and the rate capability can be improved. In patent CN110668509A, a selenium-coated high-nickel ternary layered positive electrode material and a preparation method thereof are disclosed, wherein a metal-Se bond is formed between Se atoms and metals in the ternary material to form a tightly coated layer, and the coated layer can inhibit the reaction of the positive electrode material and electrolyte. In addition, the selenium coating has higher electric conductivity, which is beneficial to electronic conduction. Therefore, the selenium coating is beneficial to the improvement of the cycle performance and the rate capability of the material.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the lithium nickel cobalt aluminate has low cycle stability, poor rate capability and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the niobium-doped nickel cobalt lithium aluminate anode material is characterized by comprising the following steps of:
step 1): sequentially adding a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source into deionized water, and uniformly mixing to form a suspension;
step 2): grinding the suspension to obtain slurry;
step 3): spray drying the slurry to obtain a precursor of the niobium-doped nickel-cobalt lithium aluminate lithium battery anode material;
step 4): and (3) putting the precursor into a crucible, putting the crucible into a tube furnace, and calcining the precursor in an oxygen atmosphere to obtain the niobium-doped lithium battery anode material.
Preferably, in the step 1), the molar ratio of corresponding elements lithium, nickel, cobalt, aluminum and niobium in the lithium source, the nickel source, the cobalt source, the aluminum source and the niobium source is 1: (0.845-0.65):0.1:0.05:(0.005-0.2).
Preferably, the lithium source in step 1) is any one or more of lithium hydroxide, lithium fluoride, lithium carbonate and lithium nitrate; the nickel source is any one or more of nickel nitrate, nickel carbonate, nickel oxide and nickel oxalate; the cobalt source is any one or more of cobalt sulfate, cobalt chloride, cobalt oxide and cobalt carbonate; the aluminum source is any one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum oxide; the niobium source is niobium oxide or niobium fluoride.
Preferably, the grinding in the step 2) adopts a sand mill, the grinding medium is zirconia balls, the rotation speed of the grinding is 1500-.
Preferably, the zirconia balls have a diameter of 0.2 mm; the particle size of the obtained slurry was 150-190 nm.
Preferably, the temperature of the calcination in the step 4) is 700-900 ℃, and the time is 15 h.
The niobium-doped nickel cobalt lithium aluminate cathode material prepared by the invention is suitable for being used under 4.5V, and has a chemical formula of LiNi0.85-xNbxCo0.10Al0.05O2(x is more than or equal to 0 and less than or equal to 0.5). The crystal structure of the material is a hexagonal crystal system, and a space group R-3 m.
The nickel-cobalt lithium aluminate lithium battery anode material is obtained by solid-phase sintering, and structural distortion and structural collapse of the material in the charge and discharge process can be inhibited by utilizing the strong chemical bond of the Nb-O bond. Thereby enhancing the capacity retention rate and rate capability of the material.
Drawings
FIG. 1 is an XRD pattern of a lithium nickel cobalt aluminate cathode material obtained in example 1;
FIG. 2 is a SEM image of the lithium nickel cobalt aluminate cathode material obtained in example 1;
FIG. 3 is the charge-discharge curve of the lithium nickel cobalt aluminate cathode material obtained in example 1;
FIG. 4 is a cycle curve of the lithium nickel cobalt aluminate positive electrode material obtained in example 1;
fig. 5 is a rate characteristic curve of the nickel cobalt lithium aluminate positive electrode material obtained in example 1.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The preparation and electrochemical performance test method of the battery comprises the following steps:
(1) preparing a battery positive plate:
uniformly mixing the obtained niobium-nickel-cobalt-doped lithium aluminate powder as the lithium ion positive electrode material, conductive carbon powder and an organic binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, adding a proper amount of solvent NMP, fully stirring to form viscous slurry, uniformly coating the viscous slurry on the surface of an aluminum foil, drying in a vacuum drying oven at 120 ℃ for 12 hours, and rolling to obtain a positive electrode plate.
(2) Battery assembly and performance testing:
the electrochemical performance of the resulting lithium nickel cobalt aluminate cathode material was evaluated using a 2016 type button cell. And stamping the rolled battery pole piece into a wafer with the diameter of 12mm, accurately weighing the mass of the wafer, calculating the mass of the nickel-cobalt lithium aluminate in the pole piece according to the formula composition, and assembling the wafer into a testable button battery in a glove box filled with argon.
The specific capacity test of the battery was performed using a battery tester (Land2000) by wuhan blue electricity corporation. Multiple charge and discharge tests were performed at 0.5C.
Example 1
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.845:0.1:0.05:0.005 ingredients, and then sequentially adding into deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 1500r/min, and grinding for 2 hours to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 750 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The nickel cobalt lithium aluminate cathode material obtained as described above was tested using an X-ray apparatus (TD-3000, Dandongtong) and the results are shown in FIG. 1. it can be seen that all diffraction peaks can be calibrated to the hexagonal system (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The morphology of the nickel cobalt lithium aluminate positive electrode material obtained above was observed by using a scanning electron microscope (japanese electron 6700F), and the result is shown in fig. 2. As can be seen from FIG. 2, the particles with the initial particle size of about 100-400nm are small and uniform, the dispersion is good, and the conductivity of the cathode material can be effectively improved.
The obtained lithium ion battery anode material is doped with niobium nickel cobalt lithium aluminate, a button cell is assembled by using a half-cell method, and a charge-discharge test is carried out under the multiplying power of 0.5, and the first discharge capacity is 192mAh/g as seen from a charge-discharge curve shown in figure 3. It can be seen from the cycle curve of fig. 4 that the discharge capacity was 180.8mAh/g after 100 cycles. The capacity retention rate after 100 cycles at 0.5C magnification was 94.16%, and the energy density was 739.3 Wh/kg. From the multiplying power of fig. 5, the specific discharge capacity of the material under 5C can reach 156.2mAh/g, which is 81.4% of the specific discharge capacity of 202.7mAh/g under 0.5C. Test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in the embodiment 1 has good capacity retention rate and rate capability when working under 4.5V, and has commercial application value.
Example 2
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.845:0.1:0.05:0.005 ingredients, and then sequentially adding into deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2000r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 800 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material obtained in example 2 was examined using an X-ray apparatus (TD-3000, danton da) and the examination result was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery anode material obtained in the example 2 was doped with niobium nickel cobalt lithium aluminate, and assembled into a button cell by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 192.8 mAh/g. After 100 cycles, the discharge capacity was 176.5 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 91.54%. The energy density was 734.1 Wh/kg. The test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in the example 2 has good electrochemical performance and commercial application value when working under 4.5V.
Example 3
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.845:0.1:0.05:0.005 ingredients, and then sequentially adding into deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2500r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder at 900 ℃ for 15 hours to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material obtained in example 3 was examined using an X-ray apparatus (TD-3000, danton da) and the examination result was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery anode material obtained in the example 3 was doped with niobium nickel cobalt lithium aluminate, and assembled into a button cell by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 198.5 mAh/g. After 100 cycles, the discharge capacity was 179.65 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 90.40%, and the energy density was 735.6 Wh/kg. The test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in the example 3 has good electrochemical performance and commercial application value when working under 4.5V.
Example 4
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.84:0.1:0.05:0.01, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 1500r/min, and grinding for 2 hours to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 800 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material obtained in example 4 was examined using an X-ray apparatus (TD-3000, danton da) and the examination result was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery anode material obtained in the example 4 was doped with niobium nickel cobalt lithium aluminate, and a button cell was assembled by using a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 190.5 mAh/g. After 100 cycles, the discharge capacity was 179.65 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 94.30%, and the energy density was 734.3 Wh/kg. The test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in the example 4 has good electrochemical performance and commercial application value when working under 4.5V.
Example 5
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.84:0.1:0.05:0.01, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2000r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder at 900 ℃ for 15 hours to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The lithium nickel cobalt aluminate cathode material obtained in example 5 was examined using an X-ray apparatus (TD-3000, Dandongtong, Inc.) and the examination result was similar to that of FIG. 1. the cathode material was also designated as hexagonal system (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery anode material obtained in example 5 was doped with niobium nickel cobalt lithium aluminate, and assembled into a button cell by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 196.7 mAh/g. After 100 cycles, the discharge capacity was 185.4 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 94.39%, and the energy density was 737.6 Wh/kg. These test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in example 5 has good electrochemical performance and commercial application value when working at 4.5V.
Example 6
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.84:0.1:0.05:0.01, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2500r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 700 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material obtained in example 6 was examined using an X-ray apparatus (TD-3000, danton da) and the examination result was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery anode material obtained in example 6 was doped with niobium nickel cobalt lithium aluminate, and assembled into a button cell by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 194.5 mAh/g. After 100 cycles, the discharge capacity was 180.7 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 92.91%, and the energy density was 729.9 Wh/kg. These test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in example 6 has good electrochemical performance and commercial application value when working at 4.5V.
Example 7
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.82:0.1:0.05:0.02, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 1500r/min, and grinding for 2 hours to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder at 900 ℃ for 15 hours to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material of example 7 was examined using an X-ray apparatus (TD-3000, danton da) and the examination was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery positive electrode material obtained in example 7 was doped with niobium nickel cobalt lithium aluminate, and a button cell was assembled by using a half cell method, and the first discharge capacity was measured at 0.5mAh/g by charge-discharge testing. After 100 cycles, the discharge capacity was 173.8 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 91.23%, and the energy density was 733.7 Wh/kg. These test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in example 7 has good electrochemical performance and commercial application value when working at 4.5V.
Example 8
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.84:0.1:0.05:0.01, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a ball mill, controlling the rotating speed to 2000r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 700 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material obtained in example 8 was examined using an X-ray apparatus (TD-3000, Dandongtong) and the examination result was similar to that of FIG. 1. the cathode material was also designated as hexagonal (α -NaFeO)2) Diffraction peak (R-3m space group) of (A), no impurity peak appeared。
The lithium ion battery positive electrode material obtained in example 8 was doped with niobium nickel cobalt lithium aluminate, and a button cell was assembled by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 196.5 mAh/g. After 100 cycles, the discharge capacity was 176.2 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 89.79%, and the energy density was 720.1 Wh/kg. These test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in example 8 has good electrochemical performance and commercial application value when working at 4.5V.
Example 9
A preparation method of a niobium element doped nickel cobalt lithium aluminate anode material specifically comprises the following steps:
(1) firstly, a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source are mixed, wherein the molar ratio of lithium, nickel, cobalt, aluminum and niobium is 1: 0.84:0.1:0.05:0.01, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2500r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain the precursor of the niobium-doped nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a crucible, putting the crucible into a tubular furnace, calcining the precursor powder in an oxygen atmosphere, and calcining the precursor powder for 15 hours at 800 ℃ to obtain the niobium-doped nickel cobalt lithium aluminate anode material.
The niobium-doped lithium nickel cobalt aluminate cathode material of example 9 was examined using an X-ray apparatus (TD-3000, danton da) and the examination result was similar to that of fig. 1, and the cathode material was also designated as hexagonal (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1).
The lithium ion battery positive electrode material obtained in example 9 was doped with niobium nickel cobalt lithium aluminate, and a button cell was assembled by a half-cell method, and a charge-discharge test was performed at 0.5 rate, and the first discharge capacity was 195.5 mAh/g. After 100 cycles, the discharge capacity was 176 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 90.26%, and the energy density was 725.6 Wh/kg. These test results show that the niobium-doped nickel cobalt lithium aluminate cathode material obtained in example 9 has good electrochemical performance and commercial application value when working at 4.5V.
Comparative example 1
The preparation method of the nickel cobalt lithium aluminate anode material without niobium doping comprises the following steps:
(1) firstly, mixing a lithium source, a nickel source, a cobalt source and an aluminum source, wherein the molar ratio of lithium, nickel, cobalt and aluminum is 1: 0.85:0.1:0.05, and then sequentially adding deionized water to be uniformly mixed to form a suspension.
(2) And adding the suspension into a sand mill, controlling the rotating speed to be 2500r/min, and grinding for 2h to obtain slurry with the particle size of 180 nm.
(3) And (3) carrying out spray drying on the slurry at 180 ℃ to obtain a precursor of the nickel-cobalt lithium aluminate anode material.
(4) And (3) putting the precursor powder into a porcelain boat, putting the porcelain boat into a tubular furnace, calcining the porcelain boat in an oxygen atmosphere, and calcining the porcelain boat for 15 hours at 900 ℃ to obtain the nickel cobalt lithium aluminate anode material.
The lithium nickel cobalt aluminate cathode material obtained in comparative example 9 was examined using an X-ray apparatus (TD-3000, Dandongtong, Inc.) and the examination result was similar to that of FIG. 1. the cathode material was also designated as hexagonal system (α -NaFeO)2) No impurity peak was observed in the diffraction peak (R-3m space group) of (1). The nickel cobalt lithium aluminate anode material synthesized by the materials is subjected to electron microscope scanning (Japanese Electron 6700F), and the test result is similar to that in the second figure.
The lithium ion battery anode material nickel cobalt lithium aluminate obtained in the comparative example 1 is assembled into a button cell by a half-cell method, and a charge-discharge test is carried out at 0.5 multiplying power, so that the first discharge capacity is 202.7 mAh/g. After 100 cycles, the discharge capacity was 141.3 mAh/g. The capacity retention rate after 100 cycles at 0.5C magnification was 69.71%, and the energy density was 788.9 Wh/kg. The discharge specific capacity under 5C can reach 110.5mAh/g, which is 52.5 percent of the discharge specific capacity under 0.1C, which is 210.5 mAh/g. The test results show that the niobium-doped nickel cobalt lithium aluminate anode material obtained in the comparative example 1 has extremely fast capacity attenuation when working under 4.5V, does not meet the industrial requirements of lithium ion batteries and needs to be modified.
The crystal structure of the layered positive electrode is stabilized by the strong chemical bond of the Nb-O bond, the phase change in the charge and discharge process is inhibited, the cycling stability of the material is improved, and the capacity retention rate of the material is improved. The Nb-doped nickel cobalt lithium aluminate prepared by the invention has initial gram capacity of about 190-200mAh/g under the multiplying power of 0.5C, and the capacity retention rate after 100 cycles is more than 90%. While the capacity retention of the sample without niobium addition is less than 70% under the same conditions. In comparison, the 4.5V niobium-doped nickel cobalt lithium aluminate cathode material provided by the invention has good commercial value.

Claims (6)

1. The preparation method of the niobium-doped nickel cobalt lithium aluminate anode material is characterized by comprising the following steps of:
step 1): sequentially adding a lithium source, a nickel source, a cobalt source, an aluminum source and a niobium source into deionized water, and uniformly mixing to form a suspension;
step 2): grinding the suspension to obtain slurry;
step 3): spray drying the slurry to obtain a precursor of the niobium-doped nickel-cobalt lithium aluminate lithium battery anode material;
step 4): and (3) putting the precursor into a crucible, putting the crucible into a tube furnace, and calcining the precursor in an oxygen atmosphere to obtain the niobium-doped lithium battery anode material.
2. The method for preparing the niobium-doped lithium nickel cobalt aluminate cathode material as claimed in claim 1, wherein the molar ratio of the corresponding elements lithium, nickel, cobalt, aluminum and niobium in the lithium source, the nickel source, the cobalt source, the aluminum source and the niobium source in step 1) is 1: (0.845-0.65):0.1:0.05:(0.005-0.2).
3. The method for preparing the niobium-doped lithium nickel cobalt aluminate cathode material as claimed in claim 1 or 2, wherein the lithium source in the step 1) is any one or more of lithium hydroxide, lithium fluoride, lithium carbonate and lithium nitrate; the nickel source is any one or more of nickel nitrate, nickel carbonate, nickel oxide and nickel oxalate; the cobalt source is any one or more of cobalt sulfate, cobalt chloride, cobalt oxide and cobalt carbonate; the aluminum source is any one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and aluminum oxide; the niobium source is niobium oxide or niobium fluoride.
4. The method as claimed in claim 1, wherein the step 2) of grinding is performed by a sand mill, the grinding medium is zirconia balls, the rotation speed of the grinding is 1500-.
5. The method of claim 1, wherein the zirconia balls have a diameter of 0.2 mm; the particle size of the obtained slurry was 150-190 nm.
6. The method for preparing the niobium doped lithium nickel cobalt aluminate cathode material as claimed in claim 1, wherein the calcination temperature in the step 4) is 700-900 ℃ and the calcination time is 15 h.
CN202010492445.1A 2020-06-03 2020-06-03 Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material Pending CN111653765A (en)

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