CN113851617A - Double-metal-element co-coated lithium cobaltate material and preparation method thereof - Google Patents

Double-metal-element co-coated lithium cobaltate material and preparation method thereof Download PDF

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CN113851617A
CN113851617A CN202010599688.5A CN202010599688A CN113851617A CN 113851617 A CN113851617 A CN 113851617A CN 202010599688 A CN202010599688 A CN 202010599688A CN 113851617 A CN113851617 A CN 113851617A
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lithium
yttrium
aluminum
cobalt
lithium cobaltate
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沈恋
董振涛
魏卫
白珍辉
朱卫泉
苏迎春
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Tianjin Guoan Mengguli New Material Technology Co ltd
RiseSun MGL New Energy Technology Co Ltd
Tianjin Guoan MGL New Materials Technology Co Ltd
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Tianjin Guoan Mengguli New Material Technology Co ltd
CITIC Guoan Mengguli Power Technology Co Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/485—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a bimetallic element co-coated lithium cobaltate material and a preparation method thereof. The bi-metal element co-coated lithium cobaltate material still has higher discharge specific capacity and excellent capacity retention rate under high pressure. The preparation method has the advantages of simple process, high yield, low energy consumption, contribution to industrial production and wide application prospect.

Description

Double-metal-element co-coated lithium cobaltate material and preparation method thereof
Technical Field
The invention belongs to the field of lithium ion battery anode materials, and particularly relates to a lithium cobaltate material co-coated with a bimetallic element and a preparation method thereof.
Background
With the rapid development of high-precision technologies such as current communication equipment and hybrid electric vehicles, the requirements of people on the performance of batteries are continuously improved, and the research and development of batteries with high capacity, long cycle and high multiplying power are the research hotspots in the field of batteries at present. Lithium ion batteries have many advantages compared to other secondary batteries, and play an important role in many fields of people's social life.
Lithium cobaltate has the advantages of easy preparation, high energy density, good cycle performance and safety performance and the like as a lithium ion battery anode material, and is widely applied to portable electronic equipment such as electronic products of mobile phones, notebook computers, digital cameras and the like. However, with the development of science and technology, 3C electronic products are gradually developed toward small size and light weight. This puts higher demands on the energy density, cycle life and other properties of the lithium cobaltate material. Therefore, it is of great significance to further develop lithium cobaltate materials with high voltage, high capacity and high cycle performance.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the lithium cobaltate material is coated by a lithium source, a cobalt source, an aluminum-containing compound and an yttrium-containing compound through a solid-phase sintering method, so that the bimetallic element co-coated lithium cobaltate material is prepared. The bimetallic element co-coated lithium cobaltate material still has high specific discharge capacity and capacity retention rate under high pressure, and the preparation method has the advantages of simple process and high yield, and is beneficial to industrial production.
The first aspect of the invention provides a bimetallic element co-coated lithium cobaltate material, which is prepared by sintering a lithium source, a cobalt source, an aluminum-containing compound and an yttrium-containing compound twice.
A second aspect of the present invention provides a method for preparing a lithium cobaltate material co-coated with a bimetallic element according to the first aspect of the present invention, the method comprising the steps of:
step 1, uniformly mixing and sintering a weighed lithium source and a weighed cobalt source to prepare a lithium cobaltate positive electrode material;
step 2, adding the weighed aluminum-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing;
and 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
The preparation method provided by the invention and the product prepared by the method have the following advantages:
(1) according to the invention, compounds containing aluminum and yttrium are directly used as coating raw materials, and a solid phase method is adopted to sinter lithium cobaltate at high temperature, so that the preparation method is simple, high in yield, more beneficial to industrial production and wide in application prospect;
(2) the capacity and the cycle performance of the aluminum-yttrium co-coated lithium cobaltate material prepared by the invention are superior to those of the traditional lithium cobaltate material (which is not subjected to aluminum/yttrium co-coating);
(3) the lithium cobaltate cathode material co-coated by the bimetallic element has higher capacity retention rate and discharge specific capacity.
Drawings
FIG. 1 shows an SEM image of a material prepared according to example 1 of the present invention;
FIG. 2 shows an SEM image of a material prepared in example 2 of the present invention;
FIG. 3 shows an SEM image of a material prepared according to example 3 of the present invention;
FIG. 4 shows an SEM image of a material prepared according to example 4 of the present invention;
FIG. 5 shows an SEM image of a material prepared according to comparative example 1 of the present invention;
FIG. 6 shows an SEM image of a material prepared according to comparative example 2 of the present invention;
FIG. 7 shows an SEM image of a material prepared in comparative example 3 of the present invention;
FIG. 8 shows a graph of the capacity retention at 4.6V0.5C for the materials prepared in comparative examples 1, 2, 3 and 4 of the present invention;
fig. 9 shows a graph of specific discharge capacity at different voltages and currents for the materials prepared in comparative examples 1, 2, 3 and 4 according to the present invention.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the invention provides a bimetallic element co-coated lithium cobaltate material, which is prepared by sintering a lithium source, a cobalt source, an aluminum-containing compound and an yttrium-containing compound twice.
The lithium source is selected from one or more of lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium oxide, lithium carbonate and lithium hydroxide; preferably, the lithium source is selected from one or more of lithium hydroxide, lithium carbonate and lithium oxide; more preferably, the lithium source is selected from one or more of lithium carbonate and lithium hydroxide.
The cobalt source is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobaltosic oxide, cobalt hydroxide, cobalt carbonate and cobalt chloride; preferably, the cobalt source is selected from one or more of cobalt hydroxide, cobalt carbonate and cobaltosic oxide; more preferably, the cobalt source is tricobalt tetraoxide.
The aluminum-containing compound is selected from one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, aluminum metaphosphate and aluminum phosphate; preferably, the aluminum-containing compound is selected from one or more of aluminum hydroxide, aluminum oxide and aluminum phosphate; more preferably, the aluminium-containing compound is selected from one or both of aluminium oxide and aluminium hydroxide.
The yttrium-containing compound is one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide, yttrium hydroxide, yttrium fluoride, yttrium nitrate, yttrium isopropoxide and yttrium iodide; preferably, the yttrium-containing compound is selected from one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide and yttrium hydroxide; more preferably, the yttrium-containing compound is selected from one or more of yttrium phosphate, yttrium metaphosphate and yttrium oxide.
Tests show that the lithium cobaltate positive electrode material is coated by using the aluminum-containing compound and the yttrium-containing compound as coating raw materials, and the prepared double-metal element co-coated lithium cobaltate material still has higher specific discharge capacity and excellent cycle performance under high voltage, which probably results from the fact that the surface stability of the material is greatly improved due to the coating layer formed by sintering the aluminum-containing compound and the yttrium-containing compound at high temperature, and thus the electrochemical performance of the material is improved.
The molar ratio of lithium element in the lithium source, cobalt element in the cobalt source, aluminum element in the aluminum-containing compound and yttrium element in the yttrium-containing compound is (0.9-1.2): 1: (0.00001-0.0001): (0.000001 to 0.00002); preferably (0.9-1.2): 1: (0.00002-0.00007): (0.000005 to 0.000015); more preferably (1.0 to 1.2): 1: (0.00002-0.00004): (0.000005 to 0.00001). Experiments show that when the molar ratio of the lithium element in the lithium source, the cobalt element in the cobalt source, the aluminum element in the aluminum-containing compound and the yttrium element in the yttrium-containing compound is (0.9-1.2): 1: (0.00001-0.0001): (0.000001-0.00002), the prepared anode material has better electrochemical performance.
The median particle diameter of the bimetallic element co-coated lithium cobaltate material is 5-19 mu m.
The bi-metal element co-coated lithium cobaltate material has a 25 ℃ voltage of 4.6V, a 0.5C capacity retention rate of 87-95% after 50 cycles, a 25 ℃ voltage of 4.5V, a 0.1C discharge specific capacity of 185-190 mAh/g, a 25 ℃ voltage of 4.6V, a 0.5C discharge specific capacity of 206-210 mAh/g, a 25 ℃ voltage of 4.6V and a 0.1C discharge specific capacity of 215-218 mAh/g.
In the invention, the bimetallic element co-coated lithium cobaltate material is prepared by a method comprising the following steps:
step 1, uniformly mixing and sintering a weighed lithium source and a weighed cobalt source to prepare a lithium cobaltate positive electrode material;
step 2, adding the weighed cobalt-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing;
and 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
In the step 1, the median particle size of the lithium cobaltate positive electrode material is 5-19 μm.
The median particle size refers to the particle size corresponding to the cumulative percentage of particle size distribution of a sample of 50%, i.e., the particle size is greater than 50% of the particles and less than 50% of the particles, and is usually used to represent the average particle size of the powder.
In the step 2, the aluminum-containing compound, the yttrium-containing compound and the lithium cobaltate positive electrode material are uniformly mixed in a high-speed mixer at the rotating speed of 800 r/min-1500 r/min.
In the step 3, the sintering is carried out in two sections, including medium-temperature sintering and high-temperature sintering;
the medium-temperature sintering temperature is 400-600 ℃, and the medium-temperature sintering time is 2-4 h.
The high-temperature sintering temperature is 700-1200 ℃, and the high-temperature sintering time is 4-12 h.
A second aspect of the present invention provides a method for preparing a bimetallic element co-coated lithium cobaltate material according to the first aspect of the present invention, the method comprising the steps of:
step 1, uniformly mixing and sintering a weighed lithium source and a weighed cobalt source to prepare a lithium cobaltate positive electrode material;
step 2, adding the weighed aluminum-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing;
and 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
This step is specifically described and illustrated below.
Step 1, uniformly mixing and sintering the weighed lithium source and cobalt source to obtain the lithium cobaltate cathode material.
The lithium source is selected from one or more of lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium oxide, lithium carbonate and lithium hydroxide; preferably, the lithium source is selected from one or more of lithium hydroxide, lithium carbonate and lithium oxide; more preferably, the lithium source is selected from one or more of lithium carbonate and lithium hydroxide.
The cobalt source is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobaltosic oxide, cobalt hydroxide, cobalt carbonate and cobalt chloride; preferably, the cobalt source is selected from one or more of cobalt hydroxide, cobalt carbonate and cobaltosic oxide; more preferably, the cobalt source is tricobalt tetraoxide.
The molar ratio of the lithium element in the lithium source to the cobalt element in the cobalt source is (0.9-1.2): 1; preferably, the molar ratio of the lithium element in the lithium source to the cobalt element in the cobalt source is (1.0-1.1): 1; more preferably, the molar ratio of the lithium element in the lithium source to the cobalt element in the cobalt source is (1.0-1.05): 1.
in the present invention, the addition amount of each raw material should be controlled within a proper range, and if the addition amount of the lithium source is insufficient, lithium diffused into the material is insufficient, so that the capacity of the finally manufactured battery is reduced; if the amount of the lithium source added is too large, the cycle retention of the positive electrode material may be lowered. When the lithium source and the cobalt source are added according to the above molar ratio, the resulting material has a higher specific discharge capacity and excellent cycle performance.
And (3) placing the weighed lithium source and cobalt source into a high-speed mixer to be uniformly mixed, wherein the rotating speed of the mixer is 1200 r/min-2000 r/min, preferably 1200 r/min-1600 r/min, and more preferably 1400 r/min. If the stirring speed is too slow, the preparation efficiency is low, the stirring effect is poor, and if the stirring speed is too fast, the device is easy to be unstable.
The stirring time is 10-45 min, preferably 15-30 min, and more preferably 20 min. The stirring time is matched with the stirring speed, if the stirring time is too short, the mixing is not uniform, the electrochemical performance of the finally prepared product is influenced, and if the stirring time is too long, the preparation efficiency is reduced.
The sintering is carried out in an oxygen or air atmosphere. Preferably under an air atmosphere.
Sintering is carried out in a muffle furnace, and the sintering is divided into medium-temperature sintering and high-temperature sintering, wherein the medium-temperature sintering temperature is 450-800 ℃, preferably 600-800 ℃, and more preferably 700-800 ℃. Tests show that the lithium cobaltate positive electrode material prepared by twice sintering has more excellent cycle performance and discharge specific capacity.
The medium-temperature sintering time is 2-4 h, preferably 2.5-4 h, and more preferably 2.5-3.5 h.
The intermediate-temperature sintering temperature and time can affect the electrochemical performance of the finally prepared material, if the intermediate-temperature sintering temperature is too low, the intermediate-temperature sintering temperature cannot reach the decomposition temperature of a lithium source, and the amount of lithium decomposed and diffused into the material is too small, so that the capacitance of the material is reduced; if the medium-temperature sintering time is too short, the lithium source cannot be fully decomposed, and the amount of lithium diffused into the material is too small, so that the capacitance of the material is reduced; when the intermediate temperature sintering temperature is 450-700 ℃ and the sintering time is 2-4 h, the finally prepared material has better electrochemical performance.
The heating rate is 3 ℃/min to 7 ℃/min, preferably 3 ℃/min to 6 ℃/min, and more preferably 3.5 ℃/min to 4.5 ℃/min.
If the temperature rise rate is too high, the reaction in the material is too violent, and the crystal growing in the later period is easy to generate defects, so that the electrochemical performance of the finally prepared anode material is not improved.
The high-temperature sintering temperature is 800-1000 ℃, preferably 850-1000 ℃, and more preferably 900-980 ℃.
The high-temperature sintering time is 4-8 h, preferably 5.5-8 h, and more preferably 6-7.5 h.
The high-temperature sintering temperature and time can influence the electrochemical performance of the finally prepared material, and in the test process, the sintering time is too short if the sintering temperature is too low, so that the crystal structure of the lithium cobaltate anode material is incompletely grown and impurity phases are generated, the stability of the battery in the charging and discharging process is poor, and the electrochemical performance is reduced; if the sintering temperature is too high and the sintering time is too long, secondary crystallization may be caused, and the specific surface area of the cathode material is reduced, resulting in reduction of capacitance.
The heating rate is 1 to 4 ℃/min, preferably 1 to 3 ℃/min, and more preferably 1 to 2 ℃/min.
If the temperature rise rate is too fast, the growth of the crystal structure of the lithium cobaltate positive electrode material is not facilitated, the crystallinity of the lithium cobaltate positive electrode material is low, and the electrochemical performance of the finally prepared material is reduced; if the temperature rise rate is too slow, the sintering time required by the material is longer, and the preparation efficiency is reduced.
And crushing and sieving the sintered product to obtain the lithium cobaltate cathode material with a certain particle size. The crushing is preferably mechanical crushing, and more preferably crushing is performed by sequentially passing through a jaw crusher, a pair of rollers and an airflow crusher.
And (4) sieving the crushed product, preferably sieving the crushed product by using a 300-mesh sieve to obtain the lithium cobaltate cathode material. The lithium cobaltate positive electrode material has a median particle diameter of 5 to 19 μm, preferably 7 to 18 μm, and more preferably 9 to 17 μm.
Tests show that the particle size of the lithium cobaltate cathode material is related to the electrochemical performance of the prepared final material. If the particle size of the lithium cobaltate positive electrode material is too large, the electrical property of the finally prepared material is reduced, which may be caused by the fact that the particle size of the lithium cobaltate material is too large, so that the specific surface area of the material is reduced, the effective contact area with an electrolyte is reduced, the electrical conductivity of the material is reduced, the amount of the reacted effective lithium ions is reduced, and the capacitance of the material is correspondingly reduced; if the particle size of the lithium cobaltate positive electrode material is too small, the specific surface area of the positive electrode material is increased, the contact area of the positive electrode material and the electrolyte is increased, the dissolution of cobalt is increased, the attenuation speed of the capacitance of the finally prepared material is increased, and the rate capability is reduced. When the median particle size of the lithium cobaltate positive electrode material is 5-19 mu m, the prepared final material has higher capacity retention rate and discharge specific capacity.
And 2, adding the weighed aluminum-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing.
The aluminum-containing compound is selected from one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, aluminum metaphosphate and aluminum phosphate; preferably, the aluminum-containing compound is selected from one or more of aluminum hydroxide, aluminum oxide and aluminum phosphate; more preferably, the aluminium-containing compound is selected from one or both of aluminium oxide and aluminium hydroxide.
The yttrium-containing compound is one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide, yttrium hydroxide, yttrium fluoride, yttrium nitrate, yttrium isopropoxide and yttrium iodide; preferably, the yttrium-containing compound is selected from one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide and yttrium hydroxide; more preferably, the yttrium-containing compound is selected from one or more of yttrium phosphate, yttrium metaphosphate and yttrium oxide.
The mass ratio of the aluminum-containing compound, the yttrium-containing compound and the lithium cobaltate positive electrode material in the step 1 is (0.0003-0.003): 0.0009-0.009): 1, preferably (0.0006-0.0025): 0.001-0.005): 1, and more preferably (0.0015-0.0025): 0.0013-0.002): 1.
And (2) placing the weighed aluminum-containing compound and yttrium-containing compound and the lithium cobaltate material prepared in the step (1) into a high-speed mixer to be uniformly mixed, wherein the rotating speed is 800 r/min-1500 r/min, preferably 900 r/min-1200 r/min, and more preferably 1000 r/min. If the stirring speed is too slow, the uniformity of the mixture after stirring is poor, the stirring efficiency is low, and if the stirring speed is too fast, particles of the lithium cobaltate positive electrode material can be broken, and the device can be unstable.
The stirring time is 5-45 min, preferably 15-30 min, and more preferably 25-30 min. The stirring time is matched with the stirring speed, if the stirring time is too short, the uniformity of the mixture after stirring is low, the electrochemical performance of the finally prepared product is influenced, and if the stirring time is too long, the preparation efficiency is reduced.
And 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
The sintering is carried out in an air or oxygen atmosphere; preferably, the sintering is performed under an air atmosphere.
The sintering is carried out in two sections, including medium-temperature sintering and high-temperature sintering; the inventor finds that the bi-metal element co-coated lithium cobalt oxide material prepared by sintering twice has more excellent cycle performance and discharge specific capacity in the test process.
The medium-temperature sintering temperature is 400-600 ℃, and preferably 450-600 ℃; more preferably from 450 ℃ to 550 ℃.
The sintering time is 2 to 4 hours, preferably 3 to 4 hours, and more preferably 3 to 3.5 hours.
The heating rate is 3 ℃/min to 6 ℃/min, preferably 4 ℃/min to 6 ℃/min, and more preferably 4 ℃/min to 5 ℃/min.
The high-temperature sintering temperature is 700-1200 ℃, preferably 800-900 ℃, and more preferably 850-900 ℃.
The high-temperature sintering temperature affects the electrochemical performance of the finally prepared material, and if the sintering temperature is too high, the electrical performance of the finally prepared material is reduced, which may be because the secondary crystallization is promoted due to the too high sintering temperature, so that the specific surface area of the anode material is reduced, the lithium ion is not easy to be deintercalated, and the capacitance is correspondingly reduced; if the sintering temperature is too low, the cycle performance and the specific discharge capacity of the prepared final material are also low, which may be caused by incomplete reaction and unstable growth of a crystal structure due to too low sintering temperature, so that the crystallinity of the prepared material is low, impurity phases are generated, the stability of the battery in the charging and discharging process is poor, and the electrochemical performance is reduced.
The sintering time is 4 to 12 hours, preferably 5 to 10 hours, and more preferably 7 to 9 hours.
The sintering time is matched with the sintering temperature, if the sintering time is too short, the crystal structure is not completely grown, so that the structural stability of the battery in the charging and discharging processes is poor, and the electrochemical performance is poor; if the sintering time is too long, the sintering time is prolonged, the preparation efficiency is reduced, secondary crystallization of the positive electrode material is caused, the particle size of the prepared material is too large, the specific surface area is too small, and the capacitance is reduced.
The heating rate is 1 to 3 ℃/min, preferably 2 to 3 ℃/min, and more preferably 2 to 2.5 ℃/min.
If the temperature rise rate is too fast, the growth of the crystal structure of the material is not facilitated, and the crystal structure is not completely grown, so that the electrochemical performance of the finally prepared material is reduced; if the temperature rise rate is too slow, the material sintering time is long, resulting in a decrease in preparation efficiency.
The sintered product is crushed, preferably mechanically. And (4) sieving the crushed product, preferably sieving the crushed product by using a 300-mesh sieve to obtain the lithium cobaltate material co-coated with the aluminum and the yttrium. The inventor finds that when the particle size of the aluminum yttrium co-coated lithium cobaltate material is 9-17 mu m, the battery prepared from the aluminum yttrium co-coated lithium cobaltate material has excellent electrical property, and particularly the capacity retention rate and the specific discharge capacity under high voltage are higher.
The invention has the following beneficial effects:
(1) according to the invention, aluminum-containing and yttrium-containing compounds are directly used as coating raw materials, and lithium cobaltate is sintered at high temperature by adopting a solid phase method, so that the preparation method has the advantages of simple process, high yield and wide application prospect, and opens up a new idea for industrial production;
(2) the bimetallic element co-coated lithium cobaltate material prepared by the method has better discharge specific capacity and cycle performance than the traditional (non-Al/Y co-coated) lithium cobaltate material; the capacity retention rate of the lithium cobaltate material prepared by the invention, which is used as the anode material of the lithium ion battery and circulates for 50 weeks at 25 ℃ and under the voltage of 4.6V0.5C, is improved by more than 10 percent compared with the traditional lithium cobaltate anode material, and the cycle performance of the lithium cobaltate anode material is obviously improved;
(3) the battery prepared by the lithium cobaltate material co-coated with the bimetallic element has a capacity retention rate of 90.1% after 50 cycles under the conditions that the temperature is 25 ℃ and the voltage is 4.6V;
(4) the battery prepared by the lithium cobaltate material co-coated with the bimetallic element has the highest specific discharge capacity of 186.8mAh/g at 25 ℃ and 4.6V at 25 ℃, the highest specific discharge capacity of 209.6mAh/g at 0.5C, 4.6V at 25 ℃ and 217.6mAh/g at 0.1C.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1000r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7h, and sintering. And after sintering, sequentially crushing by a jaw crusher, a double-roller crusher and a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
1000g of the obtained lithium cobaltate matrix, 2g of aluminum hydroxide and 1.3g of yttrium phosphate were added to a high-speed mixer and mixed at a rotational speed of 1200r/min for 25 min. Then heating to 500 ℃ in the air atmosphere of a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3.5h, then continuing heating to 900 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7.5h, and roasting; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material coated with the aluminum and the yttrium.
Example 2
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing for 20min at the rotating speed of 1200 r/min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7h, and sintering. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
1000g of the obtained lithium cobaltate matrix, 2.2g of alumina and 1.8g of yttrium metaphosphate were put into a high-speed mixer and mixed at a rotational speed of 1000r/min for 30 min. Then heating to 450 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4.5 ℃/min, keeping the temperature for 3.5h, then continuously heating to 890 ℃ according to the heating rate of 2.5 ℃/min, keeping the temperature for 6.5h, and roasting; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material coated with the aluminum and the yttrium.
Example 3
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1400r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7h, and sintering. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
1000g of the obtained lithium cobaltate matrix, 1.7g of alumina and 1.8g of yttrium oxide were put into a high-speed mixer and mixed at a rotational speed of 1000r/min for 30 min. Then heating to 500 ℃ under the air atmosphere in a muffle furnace at the heating rate of 4.2 ℃/min, keeping the temperature for 4h, then continuing heating to 850 ℃ at the heating rate of 2.3 ℃/min, keeping the temperature for 9h and roasting; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material coated with the aluminum and the yttrium.
Example 4
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1400r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7h, and sintering. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
1000g of the obtained lithium cobaltate matrix, 2.5g of aluminum hydroxide and 1.8g of yttrium metaphosphate were put into a high-speed mixer and mixed at a rotational speed of 1000r/min for 30 min. Then heating to 550 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 5 ℃/min, keeping the temperature for 4h, then continuing heating to 900 ℃ according to the heating rate of 2.5 ℃/min, keeping the temperature for 8h, and roasting; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material coated with the aluminum and the yttrium.
Comparative example
Example 1
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1400r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, keeping the temperature for 7h, and sintering. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
Adding 1000g of the obtained lithium cobaltate matrix into a high-speed mixer, and mixing for 20min at the rotating speed of 1200 r/min; then heating to 550 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 5 ℃/min, keeping the temperature for 4h, then continuing heating to 900 ℃ according to the heating rate of 2.5 ℃/min, keeping the temperature for 8h, and sintering; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material.
Comparative example 2
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1400r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, and keeping the temperature for 7 h. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
Adding 1000g of the obtained lithium cobaltate matrix, 2.5g of aluminum hydroxide and 1g of titanium dioxide into a high-speed mixer, and mixing for 20min at the rotating speed of 1200 r/min; then heating to 550 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 5 ℃/min, keeping the temperature for 4h, then continuing heating to 900 ℃ according to the heating rate of 2.5 ℃/min, keeping the temperature for 8h, and roasting; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required lithium cobaltate material coated with the aluminum and the titanium.
Comparative example 3
Weighing 1300g of cobaltosic oxide and 614g of lithium carbonate, adding into a high-speed mixer, and mixing at the rotating speed of 1400r/min for 20 min; then heating to 800 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 4 ℃/min, keeping the temperature for 3h, then continuing heating to 970 ℃ according to the heating rate of 2 ℃/min, and keeping the temperature for 7 h. And then crushing by a jaw crusher, crushing by a double-roller crusher, crushing by a jet mill, and finally sieving by a 300-mesh sieve to obtain the lithium cobaltate base material.
Adding 1000g of the obtained lithium cobaltate matrix and 2.6g of manganese carbonate into a high-speed mixer, and mixing for 20min at the rotating speed of 1200 r/min; then heating to 550 ℃ under the air atmosphere in a muffle furnace according to the heating rate of 5 ℃/min, keeping the temperature for 4h, then continuing heating to 900 ℃ according to the heating rate of 2.5 ℃/min, keeping the temperature for 8h, and sintering; and crushing the roasted lithium cobaltate, and sieving the crushed lithium cobaltate with a 300-mesh sieve to obtain the required manganese-coated lithium cobaltate material.
Examples of the experiments
Experimental example 1 scanning Electron microscope test
Scanning electron microscope tests were performed on the bi-metal co-coated lithium cobaltate materials prepared in examples 1, 2, 3 and 4 and the lithium cobaltate materials prepared in comparative examples 1, 2 and 3, respectively, and the results were shown in fig. 1, 2, 3, 4, 5, 6 and 7, respectively.
It can be seen from fig. 1, 2, 3, 4 and 5 that the surface of the lithium cobaltate material co-coated with aluminum/yttrium is smooth and convex.
Experimental example 2 Electrical Property test
The final products obtained in examples 1 to 4 and comparative example 1 were subjected to an electrical property test in which button cells were fabricated in a glove box filled with argon using a lithium sheet as a negative electrode and the respective prepared positive electrode materials as positive electrodes. Wherein, the testing conditions of the capacity retention rate are as follows: the test results are shown in FIG. 8 at 25 deg.C, 4.6V, 0.5C. The test conditions of the specific discharge capacity are as follows: condition 1: the voltage is 4.6V and 0.1C at 25 ℃; condition 2: the voltage is 4.6V and 0.5C at 25 ℃; condition 3: 25 ℃ and 4.5V and 0.1C. The test results are shown in fig. 9.
As can be seen from fig. 8, compared with the lithium cobaltate positive electrode material which is not coated or coated with other materials, it can be seen that the capacity retention rate of the lithium cobaltate positive electrode material which is subjected to the aluminum yttrium co-coating is better, the capacity retention rate of the lithium cobaltate positive electrode material which is not coated is only 77.6% -82.3% after 50 weeks of circulation, the capacity retention rate of the lithium cobaltate positive electrode material which is subjected to the aluminum titanium co-coating is 82.5% -85% after 50 weeks of circulation, the capacity retention rate of the lithium cobaltate positive electrode material which is subjected to the manganese coating is 75% -77.5% after 50 weeks of circulation, and the capacity retention rate of the lithium cobaltate positive electrode material which is subjected to the aluminum yttrium bimetallic element co-coating is still more than 88.5% after 50 weeks of circulation.
As can be seen from fig. 9, compared with the lithium cobaltate positive electrode material without coating or coating other materials, the lithium cobaltate positive electrode material coated with aluminum and yttrium has a higher specific discharge capacity, the lithium cobaltate positive electrode material without aluminum/yttrium coating has a voltage of 4.5V at 25 ℃, a specific discharge capacity of 184.8-185.2 mAh/g at 0.1C, a voltage of 4.6V at 25 ℃, a specific discharge capacity of 207.1-208.2 mAh/g at 0.5C, a voltage of 4.6V at 25 ℃, and a specific discharge capacity of 215.7-216.3 mAh/g at 0.1C.
The lithium cobaltate material subjected to aluminum yttrium co-coating has a voltage of 4.5V at 25 ℃, a specific discharge capacity of 0.1C of 185.8-186.8 mAh/g, a voltage of 4.6V at 25 ℃, a specific discharge capacity of 0.5C of 208.4-209.6 mAh/g, a voltage of 4.6V at 25 ℃ and a specific discharge capacity of 0.1C of 216.4-217.6 mAh/g. The specific discharge capacity of the lithium cobaltate positive electrode material is higher than that of a lithium cobaltate positive electrode material which is not coated or coated with other materials under corresponding conditions.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. The double-metal-element-co-coated lithium cobaltate material is characterized by being prepared by sintering a lithium source, a cobalt source, an aluminum-containing compound and an yttrium-containing compound twice.
2. The lithium cobaltate material co-coated with a bimetal element according to claim 1,
the lithium source is selected from one or more of lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium oxide, lithium carbonate and lithium hydroxide;
the cobalt source is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobaltosic oxide, cobalt hydroxide, cobalt carbonate and cobalt chloride;
the aluminum-containing compound is selected from one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, aluminum metaphosphate and aluminum phosphate;
the yttrium-containing compound is one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide, yttrium hydroxide, yttrium fluoride, yttrium nitrate, yttrium isopropoxide and yttrium iodide.
3. The lithium cobaltate material co-coated with a bimetal element according to claim 1,
the molar ratio of lithium element in the lithium source, cobalt element in the cobalt source, aluminum element in the aluminum-containing compound and yttrium element in the yttrium-containing compound is (0.9-1.2): 1: (0.00001-0.0001): (0.000001 to 0.00002).
4. The lithium cobaltate material co-coated with a bimetal element according to claim 1,
the bi-metal element co-coated lithium cobaltate material has a 25 ℃ voltage of 4.6V, a capacity retention rate of 87-95% after 0.5C circulation for 50 weeks, a 25 ℃ voltage of 4.5V, a 0.1C specific discharge capacity of 185-190 mAh/g, a 25 ℃ voltage of 4.6V, a 0.5C specific discharge capacity of 206-210 mAh/g, a 25 ℃ voltage of 4.6V and a 0.1C specific discharge capacity of 215-218 mAh/g.
5. The bi-metallic element co-coated lithium cobaltate material of claim 1, prepared by a method comprising:
step 1, uniformly mixing and sintering a weighed lithium source and a weighed cobalt source to prepare a lithium cobaltate positive electrode material;
step 2, adding the weighed aluminum-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing;
and 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
6. A preparation method of a bimetallic element co-coated lithium cobaltate material is characterized by comprising the following steps:
step 1, uniformly mixing and sintering a weighed lithium source and a weighed cobalt source to prepare a lithium cobaltate positive electrode material;
step 2, adding the weighed aluminum-containing compound and yttrium-containing compound into the lithium cobaltate positive electrode material prepared in the step 1, and uniformly mixing;
and 3, sintering the mixture mixed in the step 2 to obtain the lithium cobaltate material co-coated with the bimetallic element.
7. The method according to claim 6, wherein, in step 1,
the lithium source is selected from one or more of lithium acetate, lithium nitrate, lithium sulfate, lithium chloride, lithium oxide, lithium carbonate and lithium hydroxide;
the cobalt source is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobaltosic oxide, cobalt hydroxide, cobalt carbonate and cobalt chloride;
the molar ratio of the lithium element in the lithium source to the cobalt element in the cobalt source is (0.9-1.2): 1;
the median particle size of the lithium cobaltate positive electrode material is 5-19 mu m.
8. The production method according to claim 6, wherein, in step 2,
the aluminum-containing compound is selected from one or more of aluminum oxide, aluminum hydroxide, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum isopropoxide, aluminum metaphosphate and aluminum phosphate;
the yttrium-containing compound is one or more of yttrium phosphate, yttrium metaphosphate, yttrium oxide, yttrium hydroxide, yttrium fluoride, yttrium nitrate, yttrium isopropoxide and yttrium iodide.
9. The production method according to claim 8, wherein, in step 2,
the mass ratio of the aluminum-containing compound, the yttrium-containing compound and the lithium cobaltate positive electrode material in the step 1 is (0.0003-0.003): (0.0009-0.009): 1.
10. The production method according to claim 6, wherein, in step 3,
the sintering is carried out in an air or oxygen atmosphere;
the sintering is carried out in two sections, including medium-temperature sintering and high-temperature sintering;
the medium-temperature sintering temperature is 400-600 ℃, and the sintering time is 2-4 h;
the high-temperature sintering temperature is 700-1200 ℃, and the sintering time is 4-12 h.
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Application publication date: 20211228