CN109659534B - Positive electrode material, and preparation method and application thereof - Google Patents

Positive electrode material, and preparation method and application thereof Download PDF

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CN109659534B
CN109659534B CN201811550316.2A CN201811550316A CN109659534B CN 109659534 B CN109659534 B CN 109659534B CN 201811550316 A CN201811550316 A CN 201811550316A CN 109659534 B CN109659534 B CN 109659534B
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positive electrode
electrode material
carbon source
quantum dots
material according
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CN109659534A (en
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谭强强
王鹏飞
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Langfang Green Industry Technology Service Center
Institute of Process Engineering of CAS
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Langfang Green Industry Technology Service Center
Institute of Process Engineering of CAS
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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
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    • H—ELECTRICITY
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    • 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
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    • 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
    • H01M4/50—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
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    • 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
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    • H—ELECTRICITY
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    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a positive electrode material, and a preparation method and application thereof. The preparation method of the cathode material comprises the following steps: (1) mixing a carbon source, a metal salt and a solvent to obtain a mixed solution; (2) adding a base material into the mixed solution to obtain a precursor solution; (3) and carrying out microwave treatment on the precursor solution to obtain the anode material. The invention adopts the carbon quantum dots and the oxide quantum dots to modify the surface of the matrix material, and compared with the full-coverage coating in the prior art, the invention has the advantages of less coating amount, less influence on the specific capacity of the matrix material and lower cost.

Description

Positive electrode material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a positive electrode material, and a preparation method and application thereof.
Background
In recent years, the development of lithium ion batteries has been mainly directed to both high energy density and high power density. The nickel-cobalt-manganese ternary positive electrode material integrates the characteristics of high capacity, low cost, high compaction of lithium cobaltate and high safety and high stability of lithium manganate, and obtains extensive research.
At present, the main factor restricting the development of nickel-cobalt-manganese ternary cathode materials, particularly high-nickel ternary cathode materials, is the safety problem, and the nickel-cobalt-manganese ternary cathode materials are easy to cause potential safety hazards such as battery gas expansion and leakage due to the fact that the surface alkali content is too high; meanwhile, due to the structural instability of the ternary cathode material, oxygen is easy to be removed, and the oxygen reacts with a large amount of combustible organic electrolyte in the battery to cause spontaneous combustion.
CN108428873A discloses Al2O3The coated nickel-cobalt-aluminum ternary lithium ion battery positive electrode material comprises a nickel-cobalt lithium aluminate material and Al coated on the surface of the nickel-cobalt lithium aluminate material2O3The preparation method of the cathode material comprises the following steps: precursor Ni of ternary positive electrode material1-x-yCoxAly(OH)2+ySintering; adding a lithium source into the sintered product for sintering; finally, a coating material Al is added2O3Sintering to obtain the target product. The anode material prepared by the preparation method has good cycle performance, but the capacity is lower.
CN104393277B discloses a lithium ion ternary cathode material with a surface coated with metal oxide and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a metal salt solution with a positive electrode material, then adding an aqueous solution of an alkali metal hydroxide, adjusting the pH value of the solution to 7-12, filtering, drying to obtain the positive electrode material with the surface coated with the hydroxide, and further performing heat treatment to obtain the ternary positive electrode material with the surface coated with the metal oxide. In the preparation process of the cathode material, the flocculation reaction of hydroxide and metal salt is microscopically uneven, so that an even oxide coating layer is difficult to obtain, and the electrochemical performance of the obtained cathode material is poor.
CN108258226A discloses a carbon-coated ternary cathode material and a preparation method thereof, wherein the preparation method comprises the following steps: the method comprises the steps of introducing an organic carbon source into a reaction chamber by using chemical vapor deposition equipment, decomposing the organic carbon source by using a catalyst to generate a nano carbon material, depositing the nano carbon material on the surface of a ternary cathode material by vapor deposition, and uniformly distributing the nano carbon material on the surface of the ternary cathode material by ball milling to obtain the carbon-coated ternary cathode material.
Therefore, there is a need in the art to develop a cathode material that has good electrochemical properties, is simple in preparation process, and can be industrially produced.
Disclosure of Invention
Aiming at the problems of poor stability and poor safety of the ternary cathode material in the prior art, the invention aims to provide the cathode material, wherein the cathode material comprises a base material, and carbon quantum dots and oxide quantum dots which are arranged on the surface of the base material.
Due to the existence of the carbon quantum dots in the cathode material, on one hand, the cathode material is endowed with good conductivity; on the other hand, the lithium ion battery cathode material has the function of passivating crystal boundary defects, reduces the sensitivity of the surface of the material to moisture and carbon dioxide, further reduces the alkali content of the surface of the material, and improves the electrochemical performance and safety performance of the cathode material. Due to the existence of the oxide quantum dots, the stability of surface lattices can be enhanced, the electrochemical performance of the anode material is further improved, the capacity retention rate of the anode material after the anode material is circulated for 200 cycles is more than or equal to 94.3%, the rate capability is good, the 10C/1C ratio is more than or equal to 80.9%, and the discharge specific capacity at the current density of 0.2C is more than or equal to 200.2 mAh/g.
The invention adopts the carbon quantum dots and the oxide quantum dots to modify the surface of the matrix material, and compared with the full-coverage coating in the prior art, the invention has the advantages of less coating amount, less influence on the specific capacity of the matrix material and lower cost.
Preferably, the mass percentage of the carbon quantum dots in the cathode material is 0.1-3%, such as 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, etc.
When the mass percent of the carbon quantum dots in the cathode material is less than 0.1%, the obtained cathode material has poor conductivity and high alkali content, and further the obtained cathode material has poor electrochemical performance; when the mass percentage of the carbon quantum dots in the anode material is more than 3%, the specific capacity of the obtained anode material is low due to poor electrochemical activity and low capacity of the carbon material.
Preferably, the mass percentage of the oxide quantum dots in the cathode material is 0.1-3%, such as 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, etc.
When the mass percent of the oxide quantum dots in the anode material is less than 0.1%, the obtained anode material has poor surface structure stability; when the mass percentage of the oxide quantum dots in the anode material is more than 3%, the volume expansion of the oxide in the circulation process is obvious, and when the matrix material is a ternary material, the electrochemical activity of the oxide under the charge-discharge voltage of the ternary material is poor, so that the obtained anode material has poor circulation stability and low specific capacity.
Preferably, the oxide quantum dots comprise any one or a combination of at least two of alumina, zirconia, ceria, titania and vanadia, such as alumina, zirconia, ceria and the like.
Preferably, the particle size of the oxide quantum dots is 0.1-5 nm, such as 0.5nm, 1nm, 1.5nm, 2nm, 3nm, 4nm, and the like.
Preferably, the particle size of the carbon quantum dots is 0.1-5 nm, such as 0.5nm, 1nm, 1.5nm, 2nm, 3nm, 4nm, and the like.
Preferably, the matrix material comprises a nickel cobalt lithium manganate ternary positive electrode material and/or a nickel cobalt lithium aluminate ternary positive electrode material.
Preferably, the particle size of the matrix material is 5 to 15 μm, such as 6 μm, 7 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14 μm, and the like.
The invention also aims to provide a preparation method of the cathode material, which comprises the following steps:
(1) mixing a carbon source, a metal salt and a solvent to obtain a mixed solution;
(2) adding a base material into the mixed solution to obtain a precursor solution;
(3) and carrying out microwave treatment on the precursor solution to obtain the anode material.
According to the invention, the anode material is prepared by adopting a microwave pyrolysis method, the liquid-phase precursor solution is subjected to microwave treatment, then the carbon source can be decomposed on the surface of the base material to form carbon quantum dots, the metal salt can be decomposed on the surface of the base material to form oxide quantum dots, the carbon quantum dots and the oxide quantum dots can be distributed on the surface of the base material more uniformly by liquid-phase in-situ reaction, and the obtained anode material has good electrochemical performance.
Preferably, the power of the microwave treatment in step (3) is 500-3000W, such as 800W, 1000W, 1200W, 1500W, 1800W, 2000W, 2200W, 2500W, 2800W and the like.
When the microwave treatment power is less than 500W, the carbon source can not be completely decomposed on the surface of the base material to form carbon quantum dots, and the metal salt can not be completely decomposed on the surface of the base material to form oxide quantum dots, so that the carbon material and the oxide are unevenly distributed, and the electrochemical performance of the cathode material is influenced; when the microwave treatment power is more than 3000W, the reaction is too fast, and further, the temperature of the system is too fast, so that the carbon material is easily subjected to excessive oxidation or ignition.
Preferably, the microwave treatment time is 10min to 60min, such as 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, and the like.
When the microwave treatment time is less than 10min, the carbon source can not be completely decomposed on the surface of the base material to form carbon quantum dots, and the metal salt can not be completely decomposed on the surface of the base material to form oxide quantum dots, so that the carbon material and the oxide are unevenly distributed, and the electrochemical performance of the cathode material is influenced; when the microwave treatment time is longer than 60min, the carbon material is easily excessively oxidized.
Preferably, the temperature of the microwave treatment is 100 to 300 ℃, for example, 150 ℃, 200 ℃, 250 ℃, 280 ℃, and the like.
The temperature of microwave treatment is low, so that metal ions in metal salt can not enter crystal lattices of the base material, the stability of the structure of the base material is ensured, and meanwhile, the low temperature can prevent the carbon material from reducing the ternary cathode material; the metal oxide quantum dots on the surface of the ternary material can stabilize the surface lattice of the ternary anode material, prevent oxygen in the ternary material from coming out, and the obtained anode material has high structural stability.
Preferably, the atmosphere of the microwave treatment comprises an air atmosphere and/or an oxygen atmosphere.
The atmosphere in the preparation process is the atmosphere containing oxygen, so that nickel, cobalt and manganese metal ions in the matrix material are not reduced by carbon in the reaction process.
Preferably, the molar concentration of the carbon source in the mixed solution in the step (1) is 0.01-0.1 mol/L, such as 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, and the like.
When the molar concentration of the carbon source in the mixed solution is less than 0.01mol/L, the obtained anode material has low carbon coating amount, and simultaneously, the energy consumption of microwaves is increased, and the cost of the whole process is increased; when the molar concentration of the carbon source in the mixed solution is more than 0.1mol/L, the obtained cathode material is easily subjected to nonuniform carbon coating.
Preferably, the metal salt has a molar concentration of 0.01 to 0.1mol/L, such as 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, and the like.
When the molar concentration of the metal salt in the mixed solution is less than 0.01mol/L, the obtained anode material has low oxide coating amount, and simultaneously, the energy consumption of microwaves is increased, and the cost of the whole process is increased; when the molar concentration of the metal salt in the mixed solution is more than 0.1mol/L, the oxide coating in the obtained cathode material is likely to be uneven.
Preferably, the carbon source in step (1) comprises an organic carbon source, preferably any one or a combination of at least two of citric acid, succinic acid, lactic acid, acetic acid and formic acid, such as citric acid, succinic acid, lactic acid and the like.
Preferably, the metal salt includes a metal organic acid salt, preferably any one or a combination of at least two of aluminum isopropoxide, aluminum citrate, aluminum acetate, zirconium isopropoxide, zirconium citrate, zirconium acetate, tetrabutyl zirconate, cerium acetate, tetrabutyl titanate, isopropyl titanate, and vanadyl oxalate, for example, zirconium citrate, aluminum isopropoxide, aluminum citrate, aluminum acetate, and the like.
The metal salt can be dissolved in an organic solvent, and no anionic group residue is generated after decomposition.
Preferably, the solvent includes an organic solvent, preferably any one or a combination of at least two of ethanol, methanol, ethylene glycol and glycerol, such as ethanol, methanol, ethylene glycol, and the like.
Preferably, the base material in the step (2) comprises a nickel-cobalt-manganese ternary cathode material and/or a nickel-cobalt-aluminum ternary cathode material.
Preferably, the ratio of the matrix material to the total mass of the carbon source and the metal salt in the precursor solution is 10 to 1000, preferably 50 to 200, such as 50, 100, 300, 500, 600, 800, etc.
When the ratio of the matrix material to the total mass of the carbon source and the metal salt in the precursor solution is less than 10, the content of carbon quantum dots and oxide quantum dots in the obtained anode material is too high, and the specific capacity of the anode material is lower; when the ratio of the matrix material to the total mass of the carbon source and the metal salt in the precursor solution is greater than 1000, the content of carbon quantum dots and oxide quantum dots in the obtained anode material is too low to well cover the matrix material, the structural stability of the matrix material is poor, and further the electrochemical performance of the anode material is poor.
As a preferred technical scheme, the preparation method of the cathode material comprises the following steps:
(1) mixing an organic carbon source, a metal organic acid salt and an organic solvent according to the molar concentration of the organic carbon source being 0.01-0.1 mol/L and the molar concentration of the metal organic acid salt being 0.01-0.1 mol/L to obtain a mixed solution;
(2) adding a matrix material into the mixed solution according to the total mass ratio of the matrix material to the carbon source and the metal salt being 50-200 to obtain a precursor solution;
(3) and (3) carrying out microwave treatment on the precursor solution with power of 500-3000W, and treating for 10-60 min in an oxygen atmosphere at the temperature of 100-300 ℃ to obtain the anode material.
A further object of the invention is to provide the use of a positive electrode material according to one of the objects for use in the field of batteries, preferably for use in lithium ion batteries.
The fourth object of the present invention is to provide a lithium ion battery comprising the positive electrode material according to one of the objects.
Preferably, the positive electrode material of the lithium ion battery comprises the positive electrode material described in one of the purposes.
Preferably, the positive electrode material of the lithium ion battery is one of the objects.
Compared with the prior art, the invention has the following beneficial effects:
(1) due to the existence of the carbon quantum dots in the cathode material, on one hand, the cathode material is endowed with good conductivity; on the other hand, the lithium ion battery cathode material has the function of passivating crystal boundary defects, reduces the sensitivity of the surface of the material to moisture and carbon dioxide, further reduces the alkali content of the surface of the material, and improves the electrochemical performance and safety performance of the cathode material. Due to the existence of the oxide quantum dots, the stability of surface lattices can be enhanced, the electrochemical performance of the anode material is further improved, the capacity retention rate of the anode material after the anode material is circulated for 200 cycles is more than or equal to 94.3%, the rate capability is good, the 10C/1C ratio is more than or equal to 80.9%, and the discharge specific capacity at the current density of 0.2C is more than or equal to 200.2 mAh/g.
(2) The invention adopts the carbon quantum dots and the oxide quantum dots to modify the surface of the matrix material, and compared with the full-coverage coating in the prior art, the invention has the advantages of less coating amount, less influence on the specific capacity of the matrix material and lower cost.
(3) According to the invention, the anode material is prepared by adopting a microwave pyrolysis method, the liquid-phase precursor solution is subjected to microwave treatment, then the carbon source can be decomposed on the surface of the base material to form carbon quantum dots, the metal salt can be decomposed on the surface of the base material to form oxide quantum dots, the carbon quantum dots and the oxide quantum dots can be distributed on the surface of the base material more uniformly by liquid-phase in-situ reaction, and the obtained anode material has good electrochemical performance.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the cathode material comprises the following steps:
(1) mixing citric acid, zirconium citrate and ethanol according to the molar concentration of the citric acid of 0.04mol/L and the molar concentration of the zirconium citrate of 0.02mol/L to obtain a mixed solution;
(2) in terms of LiNi0.9Co0.05Mn0.05O2And the total mass ratio of the citric acid to the zirconium citrate is 100, and LiNi is added into the mixed solution0.9Co0.05Mn0.05O2Obtaining a precursor solution;
(3) and (3) carrying out microwave treatment with power of 1500W on the precursor solution, and treating for 25min in an oxygen atmosphere at the temperature of 200 ℃ to obtain the anode material.
Example 2
The difference from the example 1 is that the citric acid molar concentration in the step (1) is 0.01 mol/L.
Example 3
The difference from example 1 is that the citric acid molar concentration in step (1) is 0.1 mol/L.
Example 4
The difference from example 1 is that the citric acid molar concentration in step (1) is 0.005 mol/L.
Example 5
The difference from the example 1 is that the citric acid molar concentration in the step (1) is 0.15 mol/L.
Example 6
The difference from the example 1 is that the molar concentration of zirconium citrate in the step (1) is 0.01 mol/L.
Example 7
The difference from the example 1 is that the molar concentration of zirconium citrate in the step (1) is 0.1 mol/L.
Example 8
The difference from example 1 is that the molar concentration of zirconium citrate in step (1) is 0.005 mol/L.
Example 9
The difference from the example 1 is that the molar concentration of zirconium citrate in the step (1) is 0.15 mol/L.
Example 10
The difference from example 1 is that LiNi in step (2)0.9Co0.05Mn0.05O2The ratio to the total mass of citric acid and zirconium citrate was 10.
Example 11
The difference from example 1 is that LiNi in step (2)0.9Co0.05Mn0.05O2The ratio to the total mass of citric acid and zirconium citrate was 1000.
Example 12
The preparation method of the cathode material comprises the following steps:
(1) mixing glucose, aluminum acetate and ethylene glycol according to the molar concentration of the glucose being 0.04mol/L and the molar concentration of the aluminum acetate being 0.02mol/L to obtain a mixed solution;
(2) in terms of LiNi0.9Co0.05Mn0.05O2And the total mass ratio of the mixed solution to glucose and aluminum acetate is 100, and LiNi is added into the mixed solution0.9Co0.05Mn0.05O2Obtaining a precursor solution;
(3) and (3) carrying out microwave treatment with 500W power on the precursor solution, and treating for 60min in an air atmosphere at the temperature of 300 ℃ to obtain the anode material.
Example 13
The preparation method of the cathode material comprises the following steps:
(1) mixing lactic acid, aluminum citrate and methanol according to the molar concentration of the lactic acid of 0.04mol/L and the molar concentration of the aluminum citrate of 0.02mol/L to obtain a mixed solution;
(2) in terms of LiNi0.9Co0.05Mn0.05O2And the total mass ratio of lactic acid and aluminum citrate is 100, and LiNi is added into the mixed solution0.9Co0.05Mn0.05O2Obtaining a precursor solution;
(3) and (3) carrying out 3000W microwave treatment on the precursor solution, and treating for 10min at 100 ℃ in an air atmosphere to obtain the anode material.
Comparative example 1
The difference from example 1 is that citric acid is not added in step (1).
Comparative example 2
The difference from example 1 is that no zirconium citrate is added in step (1).
Comparative example 3
The difference from example 1 is that zirconium citrate and citric acid are not added in step (1).
Comparative example 4
The difference from example 1 is that the mass of zirconium citrate added in step (1) is LiNi added in step (2)0.9Co0.05Mn0.05O220% by mass of LiNi0.9Co0.05Mn0.05O2And carrying out full-coverage coating.
Comparative example 5
The difference from example 1 is that the mass of citric acid added in step (1) is LiNi added in step (2)0.9Co0.05Mn0.05O220% by mass of LiNi0.9Co0.05Mn0.05O2And carrying out full-coverage coating.
And (3) performance testing:
the prepared positive electrode material is subjected to the following performance tests:
(1) assembling the battery: the anode material prepared by the invention is prepared into an anode plate, a cathode is a metal lithium plate, a diaphragm is Celgard2400, and electrolyte is 1mol/L LiPF6and/DMC + DEC, assembling to obtain CR2025 button cell. The preparation process of the positive pole piece comprises the following steps: mixing the prepared positive electrode material, conductive agent acetylene black and binder PVDF (polyvinylidene fluoride) according to the mass ratio of 90:5:5, using N-methylpyrrolidone NMP as a solvent to prepare slurry, coating the slurry on an aluminum foil, drying the aluminum foil at 120 ℃ for 12 hours, and rolling and punching the aluminum foil into a wafer with the diameter of 8.4mm to be used as a positive electrode piece.
(2) Electrochemical testing: and (3) testing the prepared button cell on a LAND cell testing system of Wuhanjinuo electronic Limited company under the condition of normal temperature, wherein the charging and discharging voltage interval is 3.0-4.3V, and the 1C current density is defined to be 180 mA/g. Cycling for 200 weeks under the current density of 1C, testing the capacity retention rate, wherein the capacity retention rate of 200 weeks is the specific discharge capacity/first discharge capacity of 200 weeks; and (3) rate performance test: and charging the battery to a charge cut-off voltage by adopting a current density of 0.5C, respectively testing the discharge specific capacity of the battery under the current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C, and calculating the ratio of 10C/1C.
The performance test results are shown in table 1:
TABLE 1
Figure BDA0001910470820000111
Figure BDA0001910470820000121
As can be seen from Table 1, in examples 1 to 13, carbon quantum dots and oxide quantum dots are uniformly distributed in a matrix material LiNi0.9Co0.05Mn0.05O2The obtained anode material has good electrochemical performance, the capacity retention rate of the anode material after 200 cycles is more than or equal to 94.3 percent, and the rate performance is good, and the data in the table shows that the 10C/1C ratio is more than or equal to 80.9 percent, and the discharge specific capacity at 0.2C current density is more than or equal to 200.2 mAh/g.
As can be seen from table 1, in example 4, the rate capability (10C/1C) and the capacity retention rate at 200 cycles are lower than those in example 1, and it is possible that the molar concentration of citric acid is too small in example 4, the content of carbon quantum dots in the obtained cathode material is too small, the conductivity of the cathode material is poor, and the surface alkali content is high, so that in example 4, the rate capability (10C/1C) and the capacity retention rate at 200 cycles are lower than those in example 1.
As can be seen from table 1, in example 5, compared to example 1, the specific discharge capacity at the current density of 0.2C, 0.5C, 1C, 2C, 5C and 10C is lower, which is probably because the molar concentration of citric acid in example 5 is too large, the content of carbon quantum dots in the obtained cathode material is too high, the electrochemical activity of the carbon material is poor, the capacity is lower, and further the specific discharge capacity of the obtained cathode material is lower, so that in example 5, compared to example 1, the specific discharge capacity at the current density of 0.2C, 0.5C, 1C, 2C, 5C and 10C is lower.
As can be seen from table 1, the rate capability (10C/1C) and the capacity retention rate at 200 cycles are lower in example 8 compared with example 1, and it is probably because the molar concentration of zirconium citrate in example 8 is too small, the content of zirconium oxide quantum dots in the obtained cathode material is too small, the amount of oxygen not bonded on the surface of the ternary material is too large, and the surface structure stability of the cathode material is poor, so that the rate capability (10C/1C) and the capacity retention rate at 200 cycles are lower in example 8 compared with example 1.
As can be seen from table 1, in example 9, compared to example 1, the specific discharge capacity at the current density of 0.2C, 0.5C, 1C, 2C, 5C and 10C is lower, and the capacity retention rate at 200 cycles is lower, which is probably because the molar concentration of zirconium citrate in example 9 is too large, the content of zirconium oxide quantum dots in the obtained cathode material is too high, and the electrochemical activity of zirconium oxide is poor, so that in example 9, compared to example 1, the specific discharge capacity at the current density of 0.2C, 0.5C, 1C, 2C, 5C and 10C is lower, and the capacity retention rate at 200 cycles is lower.
As can be seen from Table 1, the rate capability (10C/1C) and the capacity retention rate at 200 weeks of comparative example 1 are lower than those of example 1, probably because the positive electrode material obtained by adding no citric acid in the comparative example 1 has no carbon quantum dots, and further has poor conductivity and high surface alkali content, so that the rate capability (10C/1C) and the capacity retention rate at 200 weeks of comparative example 1 are lower than those of example 1.
As can be seen from Table 1, the rate capability (10C/1C) and the 200-week capacity retention rate of the comparative example 2 are lower than those of the example 1, probably because the zirconium citrate is not added in the comparative example 2, and the surface structure stability of the cathode material is poor, so that the rate capability (10C/1C) and the 200-week capacity retention rate of the comparative example 2 are lower than those of the example 1.
As can be seen from Table 1, the rate capability (10C/1C) and the capacity retention rate at 200 weeks of comparative example 3 are lower than those of example 1, probably because the zirconium citrate and the citric acid are not added in the comparative example 3, and the obtained cathode material has poor surface structure stability, poor conductivity and high surface alkali content, so that the rate capability (10C/1C) and the capacity retention rate at 200 weeks of comparative example 3 are lower than those of example 1.
As can be seen from table 1, the specific discharge capacity of comparative example 4 was lower at current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C than that of example 1, probably because the positive electrode material obtained in comparative example 4 was coated with zirconium oxide in full coverage and the electrochemical activity of zirconium oxide was poor, the specific discharge capacity of comparative example 4 was lower at current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C than that of example 1.
As can be seen from table 1, the specific discharge capacity of comparative example 5 at current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C is lower than that of example 1, probably because the positive electrode material obtained in comparative example 5 was entirely coated with the carbon material, and the electrochemical activity of the carbon material was poor, the specific discharge capacity of comparative example 5 at current densities of 0.2C, 0.5C, 1C, 2C, 5C and 10C was lower than that of example 1.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (19)

1. A preparation method of a positive electrode material is characterized by comprising the following steps:
(1) mixing a carbon source, a metal salt and a solvent to obtain a mixed solution;
(2) adding a base material into the mixed solution to obtain a precursor solution;
(3) performing microwave treatment on the precursor solution to obtain a positive electrode material;
the metal salt comprises a metal organic acid salt, and the base material in the step (2) comprises a nickel-cobalt-manganese ternary positive electrode material and/or a nickel-cobalt-aluminum ternary positive electrode material; the power of the microwave treatment in the step (3) is 500-3000W; the microwave treatment time is 10 min-60 min; the temperature of the microwave treatment is 100-300 ℃; the ratio of the matrix material to the total mass of the carbon source and the metal salt in the precursor solution is 10-1000;
the anode material comprises a base material, and carbon quantum dots and oxide quantum dots which are arranged on the surface of the base material; the mass percentage of the carbon quantum dots in the positive electrode material is 0.1-3%; the mass percentage of the oxide quantum dots in the anode material is 0.1-3%.
2. The method of preparing a positive electrode material according to claim 1, wherein the oxide quantum dots comprise any one of alumina, zirconia, ceria, titania and vanadia or a combination of at least two thereof.
3. The method for preparing the positive electrode material according to claim 1, wherein the particle size of the oxide quantum dot is 0.1 to 5 nm.
4. The method for producing the positive electrode material according to claim 1, wherein the particle diameter of the carbon quantum dot is 0.1 to 5 nm.
5. The method for producing a positive electrode material according to claim 1, wherein the particle size of the matrix material is 5 to 15 μm.
6. The method for producing a positive electrode material according to claim 1, wherein an atmosphere of the microwave treatment comprises an air atmosphere and/or an oxygen atmosphere.
7. The method for preparing the positive electrode material according to claim 1, wherein the molar concentration of the carbon source in the mixed solution in the step (1) is 0.01 to 0.1 mol/L.
8. The method for producing a positive electrode material according to claim 1, wherein the molar concentration of the metal salt is 0.01 to 0.1 mol/L.
9. The method for producing a positive electrode material according to claim 1, wherein the carbon source in the step (1) comprises an organic carbon source.
10. The method for producing a positive electrode material according to claim 9, wherein the organic carbon source comprises any one of citric acid, succinic acid, lactic acid, acetic acid and formic acid or a combination of at least two thereof.
11. The method for preparing a positive electrode material according to claim 1, wherein the metal organic acid salt comprises any one of aluminum isopropoxide, aluminum citrate, aluminum acetate, zirconium isopropoxide, zirconium citrate, zirconium acetate, tetrabutyl zirconate, cerium acetate, tetrabutyl titanate, isopropyl titanate, and vanadyl oxalate, or a combination of at least two thereof.
12. The method for producing a positive electrode material according to claim 1, wherein the solvent in the step (1) comprises an organic solvent.
13. The method for preparing a positive electrode material according to claim 12, wherein the organic solvent comprises any one of ethanol, methanol, ethylene glycol, and glycerol, or a combination of at least two thereof.
14. The method for preparing a positive electrode material according to claim 1, wherein the ratio of the matrix material to the total mass of the carbon source and the metal salt in the precursor solution is 50 to 200.
15. The method for preparing the positive electrode material according to claim 1, comprising the steps of:
(1) mixing an organic carbon source, a metal organic acid salt and an organic solvent according to the molar concentration of the organic carbon source being 0.01-0.1 mol/L and the molar concentration of the metal organic acid salt being 0.01-0.1 mol/L to obtain a mixed solution;
(2) adding a matrix material into the mixed solution according to the total mass ratio of the matrix material to the carbon source and the metal salt being 50-200 to obtain a precursor solution;
(3) and (3) carrying out microwave treatment on the precursor solution with power of 500-3000W, and treating for 10-60 min in an oxygen atmosphere at 100-300 ℃ to obtain the anode material.
16. Use of a positive electrode material obtained by the method for preparing a positive electrode material according to any one of claims 1 to 15, wherein the positive electrode material is used in the field of batteries.
17. Use according to claim 16, wherein the positive electrode material is used as a positive electrode material for a lithium ion battery.
18. A lithium ion battery, characterized in that the lithium ion battery comprises the positive electrode material prepared by the preparation method of any one of claims 1 to 15.
19. The lithium ion battery according to claim 18, wherein the positive electrode material of the lithium ion battery is the positive electrode material prepared by the preparation method according to any one of claims 1 to 15.
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