CN108493406B - Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery - Google Patents

Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery Download PDF

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CN108493406B
CN108493406B CN201810167828.4A CN201810167828A CN108493406B CN 108493406 B CN108493406 B CN 108493406B CN 201810167828 A CN201810167828 A CN 201810167828A CN 108493406 B CN108493406 B CN 108493406B
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cathode material
nickel ternary
positive electrode
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CN108493406A (en
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王纯德
李明露
杨军帅
宋文锋
怀永建
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Avic Innovation Technology Research Institute Jiangsu Co ltd
China Aviation Lithium Battery Co Ltd
China Lithium Battery Technology Co Ltd
CALB Technology Co Ltd
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China Aviation Lithium Battery Research Institute 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to application of a high-nickel ternary cathode material as a catalyst in preparation of a carbon nanotube, a cathode material, a preparation method of the cathode material and a lithium battery, and belongs to the technical field of lithium ion batteries. The application of the invention comprises the following steps: placing the high-nickel ternary positive electrode material in a reaction atmosphere, and keeping the temperature at 300-490 ℃ for 1-10 h; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1‑a‑bO2、LiNixCoyAl1‑x‑yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1. The application of the invention can simplify the process of growing the carbon nano tube on the surface of the high-nickel ternary cathode material by catalyzing the cracking of the carbon source gas by the high-nickel ternary cathode material, and compared with the prior art, the invention can reduce the production cost and improve the purity of the obtained ternary material.

Description

Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery
Technical Field
The invention relates to application of a high-nickel ternary cathode material as a catalyst in preparation of a carbon nanotube, a cathode material, a preparation method of the cathode material and a lithium battery, and belongs to the technical field of lithium ion batteries.
Background
In recent years, with the large consumption of non-renewable resources such as petroleum and the support of new energy by the nation, the electric automobile industry is rapidly developed. Since the advent of electric automobiles, increasingly higher requirements have been placed on the driving mileage of vehicles and the energy density of batteries, and according to the target of "2025 made in china" published by the national program of new energy automobiles in china, the energy density of batteries is required to reach 300Wh/kg in 2020, 400Wh/kg in 2025 and 500Wh/kg in 2030. In order to achieve the higher and higher specific energy target, the most fundamental method is to break through from the electrode material, and the development of material with high specific capacity and excellent cycle performance is urgent. Compared with improvement on a negative electrode material, development of a positive electrode material with higher capacity and good cycle performance is more critical, and battery positive electrode materials adopted by most power battery production enterprises in the market at present are ternary materials of lithium iron phosphate, lithium cobaltate, lithium manganate and nickel cobalt manganese, but the materials are difficult to meet the requirements at the same time, so that development of other types of positive electrode materials, particularly high-energy-density positive electrode materials, is imperative.
Currently, in order to improve the energy density of the cathode material, the research on the high-nickel ternary cathode material is increasing, including nickel-cobalt-manganese and nickel-cobalt-aluminum materials, and in order to improve the rate capability and cycle life of the material, there are two main ways of nanocrystallization and carbon recombination. The nano-material can improve the performance of the material, but the specific surface area of the material is increased, the contact area with the electrolyte is larger, more side reactions are brought, and the performance of the battery is further influenced. Carbon recombination is an effective means for improving the electrochemical performance of the anode material, can effectively inhibit the occurrence of side reactions in the battery, improves the cycle performance, and can improve the electronic conductivity of the electrode material, reduce the polarization of the electrode and improve the rate capability of the electrode material. The carbon composite technology of the lithium iron phosphate material is quite complete and can be produced in mass, the carbon composite technology of the ternary material is yet to be further improved, and particularly the high-nickel ternary positive electrode material has a very important position in the future development process.
In addition, the performance of the electrode slurry also has a great influence on the performance of the battery, and the phenomena of particle agglomeration and uneven distribution of the carbon conductive agent in the slurry combining process are caused due to the difference of the physical and chemical properties of all components of the slurry. The uniformly dispersed electrode slurry can ensure that the internal resistance of each part of the electrode is uniform, and is beneficial to the performance of active materials in the charging and discharging processes of the battery.
In the prior art, the Chinese patent with application publication number CN101527353A discloses a preparation method of a lithium ion battery anode composite material, which firstly adopts a layered lithium nickel cobalt manganese oxide LiNi as an anode active material1/3Co1/ 3Mn1/3O2The mass ratio of the catalyst ferrocene is 100: 10, and LiNi is added1/3Co1/3Mn1/3O2Dissolving ferrocene and acetone, and mixing and stirring uniformly to prepare a mixed solution with the concentration of 10 g/ml; then heating to evaporate and remove the solvent, and preparing the single-walled carbon nanotube and LiNi by adopting a chemical vapor deposition method1/3Co1/3Mn1/3O2The composite lithium ion battery anode material. The chemical vapor deposition method is used for preparing LiNi-Co-Mn oxide1/3Co1/3Mn1/3O2The method for coating the carbon nano tube on the surface has complex process, and the obtained positive electrode material contains impurities, which influence the performance of the positive electrode material.
Disclosure of Invention
The invention aims to provide application of a high-nickel ternary cathode material as a catalyst in the aspect of preparing carbon nanotubes, and the preparation method of the carbon composite high-nickel ternary cathode material can be simplified.
The invention also provides a carbon composite ternary cathode material, a preparation method thereof and a lithium ion battery adopting the carbon composite ternary cathode material.
In order to realize the purpose, the technical scheme adopted by the application of the high-nickel ternary cathode material as the catalyst in the aspect of preparing the carbon nano tube is as follows:
the application of the high-nickel ternary cathode material as a catalyst in the aspect of preparing the carbon nano tube comprises the following steps: placing the high-nickel ternary positive electrode material in a reaction atmosphere, and keeping the temperature at 300-490 ℃ for 0.5-20 h; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
The high-nickel ternary cathode material is applied to the preparation of the carbon nano tube as the catalyst, the catalyst or a precursor of the catalyst is not required to be doped in the nickel ternary material, the high-nickel ternary cathode material is placed in a reaction atmosphere, and the pyrolysis of a carbon source gas can be realized by carrying out heat preservation at 300-490 ℃, so that the process for growing the carbon nano tube on the surface of the high-nickel ternary cathode material can be simplified, compared with the prior art, the production cost is reduced, and the purity of the obtained carbon composite high-nickel ternary cathode material is improved.
The carbon source gas is at least one of methane, ethane, acetylene and propyne.
Preferably, the reaction atmosphere further comprises a carrier gas. The flow rate of the reaction atmosphere is 8-15 mL/min, and the volume ratio of the carbon source gas to the carrier gas is 5-15: 80-100. The flow of reaction atmosphere correspondingly adopted for every 10g of the high-nickel ternary cathode material is 8-15 mL/min. The safety of the reaction can be improved by using a carrier gas. The carrier gas is Ar or N2One kind of (1).
Preferably, the flow rate of the reaction atmosphere is 10mL/min, and the volume ratio of the carbon source gas to the carrier gas is 10: 90. The flow of reaction atmosphere adopted for every 10g of the high-nickel ternary cathode material is 10 mL/min.
The particle size D of the high-nickel ternary cathode material501 to 20 μm. Further preferably, D of the high-nickel ternary cathode material50And 8 μm.
Preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.65 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, a + b is less than or equal to 1, x is more than or equal to 0.65 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and x + y is less than or equal to 1.
Further preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
Preferably, the constant temperature time is 1-10 h. The constant temperature was 400 ℃.
Further preferably, the constant temperature time is 3 hours.
The carbon composite ternary cathode material adopts the technical scheme that:
a carbon composite ternary positive electrode material comprises a high-nickel ternary positive electrode material and a carbon nano tube growing on the surface of the high-nickel ternary positive electrode material, wherein the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
The carbon composite ternary cathode material can simplify the slurry mixing process, improve the electronic conductivity of the ternary material and the uniformity of the distribution of carbon nano tubes in the slurry preparation process, further reduce the internal resistance of the lithium ion battery, inhibit the side reaction of the electrode material, and improve the capacity, the cycle performance and the rate capability of the lithium ion battery.
The mass of the carbon nano tube is 1-20% of the mass of the carbon composite ternary cathode material.
The excessive content of the carbon nano tube in the carbon composite ternary cathode material is not beneficial to the gram capacity performance of the high-nickel ternary cathode material. Further preferably, the mass of the carbon nanotube accounts for no more than 3% of the mass of the carbon composite ternary cathode material.
Preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.65 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, a + b is less than or equal to 1, x is more than or equal to 0.65 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and x + y is less than or equal to 1.
Further preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
The carbon source gas is at least one of methane, ethane, acetylene and propyne.
The particle size D of the high-nickel ternary cathode material501 to 20 μm. Further preferably, D of the high-nickel ternary cathode material50And 8 μm.
The preparation method of the carbon composite ternary cathode material adopts the technical scheme that:
a preparation method of a carbon composite ternary cathode material comprises the following steps: placing the high-nickel ternary positive electrode material in a reaction atmosphere, keeping the temperature of the high-nickel ternary positive electrode material at 300-490 ℃ for 0.5-20 hours, and cooling to obtain the high-nickel ternary positive electrode material; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
According to the preparation method of the carbon composite ternary cathode material, the carbon nano tube is generated in situ on the surface of the high-nickel ternary cathode material, so that the firmness and uniformity of the coating of the carbon nano tube on the surface of the high-nickel ternary cathode material are improved, and the performance of an active substance of the material in the charging and discharging process is favorably exerted. The preparation method is simple and reliable, and is easy for large-scale production.
Preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.65 and less than or equal to 0.9, b is more than or equal to 0.05 and less than or equal to 0.2, a + b is less than or equal to 1, x is more than or equal to 0.65 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.2, and x + y is less than or equal to 1.
Further preferably, the high-nickel ternary cathode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
The carbon source gas is at least one of methane, ethane, acetylene and propyne.
Preferably, the reaction atmosphere further comprises a carrier gas. The flow rate of the reaction atmosphere is 8-15 mL/min, and the volume ratio of the carbon source gas to the carrier gas is 5-15: 80-100. The flow of reaction atmosphere correspondingly adopted for every 10g of the high-nickel ternary cathode material is 8-15 mL/min. The carrier gas is Ar or N2One kind of (1).
Preferably, the flow rate of the reaction atmosphere is 10mL/min, and the volume ratio of the carbon source gas to the carrier gas is 10: 90. The flow of reaction atmosphere adopted for every 10g of the high-nickel ternary cathode material is 10 mL/min.
The particle size D of the high-nickel ternary cathode material501 to 20 μm. Further preferably, D of the high-nickel ternary cathode material50And 8 μm.
The content of the carbon nano tube in the carbon composite ternary cathode material is mainly determined by the constant temperature time and temperature. The content of the carbon nano tube is too small, the performance improvement of the ternary cathode material is limited, and the exertion of the battery capacity can be influenced by the excessive content of the carbon nano tube, so that the selection of proper constant temperature time and temperature has important influence on the performance of the lithium ion battery adopting the carbon composite ternary cathode material. Preferably, the constant temperature time is 1-10 h. The constant temperature was 400 ℃.
Further preferably, the constant temperature time is 3 hours.
The lithium battery adopts the technical scheme that:
a lithium battery adopting the carbon composite ternary cathode material.
The lithium battery comprises a positive plate, a diaphragm, a negative plate and electrolyte, wherein the positive plate comprises a current collector and a positive active substance layer arranged on the current collector, the positive active substance layer comprises a positive active substance, and the positive active substance comprises the carbon composite ternary positive material.
The lithium battery adopts the carbon composite ternary cathode material as the cathode active material, has good cycle energy and rate capability, and has smaller internal resistance.
The lithium battery is a lithium ion button battery, the diaphragm is a polyethylene and polypropylene composite diaphragm, and the negative plate is a lithium plate.
The electrolyte includes a lithium salt and an organic solvent. The concentration of lithium salt in the electrolyte is 0.8-2.0 mol/L.
Preferably, the positive electrode active material layer is composed of a carbon composite ternary positive electrode material and a binder; the mass of the carbon nano tube accounts for no more than 3 percent of the mass of the carbon composite ternary cathode material.
Drawings
Fig. 1 is an SEM image of the carbon composite ternary cathode material of example 1;
fig. 2 is a XRD test versus scale plot of the carbon composite ternary cathode material of example 1 and the high nickel ternary cathode material of comparative example 1;
fig. 3 is a comparative diagram of XRD test of the positive electrode materials of comparative example 1 and comparative example 2;
fig. 4 is a graph of the ac impedance measured after assembling a button cell using the positive electrode materials of example 1 and comparative example 1.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The high-nickel ternary cathode material adopted in the invention can be prepared by a liquid phase mixing and solid phase sintering method, and can also be an NCA ternary cathode material or an NCM ternary cathode material purchased through a public way. The high-nickel ternary cathode material has high nickel content and high theoretical specific capacity, and belongs to a high-energy density material.
Example 1
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is LiNi0.8Co0.15Al0.05O2The crystal grains are spherical and have a grain diameter D50Is 8 μm; the mass of the carbon nano tube is 3% of that of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 400 ℃ at the speed of 5 ℃/min, preserving heat at 400 ℃ for 3h, naturally cooling, and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
The carbon composite cathode material prepared in the embodiment is tested by a scanning electron microscope, the test result is shown in fig. 1, and the carbon nanotube of the coating layer deposited on the surface of the bare ternary material can be clearly seen from fig. 1.
Example 2
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is LiNi0.8Co0.15Al0.05O2The crystal grains are spherical and have a grain diameter D50Is 8 μm; the mass of the carbon nano tube is 1% of that of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 400 ℃ at the speed of 5 ℃/min, preserving the heat at 400 ℃ for 1h, naturally cooling and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, wherein the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
Example 3
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is LiNi0.8Co0.15Al0.05O2The crystal grains are spherical, and the grain diameter D50 is 8 mu m; mass of carbon nanotubeIs 10% of the mass of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 400 ℃ at the speed of 5 ℃/min, preserving the heat at 400 ℃ for 10h, naturally cooling and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, wherein the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
Example 4
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is LiNi0.9Co0.05Mn0.05O2The crystal grains are spherical and have a grain diameter D 5020 μm; the mass of the carbon nano tube is 20% of the mass of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary positive electrode material into a clean crucible, uniformly distributing the high-nickel ternary positive electrode material, putting the high-nickel ternary positive electrode material into a tubular furnace, and then adding the high-nickel ternary positive electrode material into the tubular furnace at a ratio of 10mL/min flow rate is introduced into Ar/C2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 490 ℃ at the speed of 5 ℃/min, preserving the heat at 490 ℃ for 20 hours, naturally cooling, and cutting off an air source to obtain the high-temperature-resistant high-temperature; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, wherein the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
Example 5
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is LiNi0.7Co0.2Mn0.1O2The crystal grains are spherical and have a grain diameter D50Is 10 μm; the mass of the carbon nano tube is 10% of that of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tube furnace to 300 ℃ at the speed of 5 ℃/min, preserving the heat at 300 ℃ for 10h, naturally cooling and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, wherein the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
Example 6
The carbon composite ternary cathode material comprises a high-nickel ternary cathode material and a carbon nano tube growing on the surface of the high-nickel ternary cathode material; the high-nickel ternary positive electrode material is made of LiNi0.82Co0.15Al0.03O2And LiNi0.65Co0.15Mn0.2O2Composition of LiNi0.82Co0.15Al0.03O2And LiNi0.65Co0.15Mn0.2O2In a mass ratio of 1:1, the crystal grains are all spherical, and the particle diameter D50Is 1 μm; the mass of the carbon nano tube is 1% of that of the carbon composite ternary cathode material.
The preparation method of the carbon composite ternary cathode material comprises the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 380 ℃ at the speed of 5 ℃/min, preserving the heat at 380 ℃ for 1h, naturally cooling and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
The lithium battery of the embodiment is a lithium ion battery and comprises a positive pole piece, a diaphragm, a negative pole piece, electrolyte and a shell; the positive pole piece comprises a current collector and a positive active substance layer adhered to the current collector, wherein the positive active substance layer consists of a positive active substance and a binder, and the mass ratio of the positive active substance to the binder is 97: 3; the positive electrode active material is the carbon composite ternary positive electrode material of the embodiment, and the binder is polyvinylidene fluoride.
Comparative example 1
Comparative example 1 was prepared using commercially available LiNi0.8Co0.15Al0.05O2The high-nickel ternary positive electrode material has spherical crystal grains and a grain diameter D50And 8 μm.
Comparative example 2
The carbon composite ternary cathode material of the comparative example was prepared by a method comprising the following steps:
1) accurately weighing 10g of high-nickel ternary cathode material according to the scale of the tube furnace; the high-nickel ternary positive electrode material is LiNi0.8Co0.15Al0.05O2The crystal grains are spherical, and the grain diameter D50 is 8 mu m;
2) putting the weighed high-nickel ternary cathode material into a clean crucible, uniformly distributing the high-nickel ternary cathode material, putting the high-nickel ternary cathode material into a tubular furnace, and introducing Ar/C at the flow rate of 10mL/min2H2Removing air in the pipeline and the hearth in a mixed atmosphere for a period of time, heating the tubular furnace to 500 ℃ at the speed of 5 ℃/min, preserving the heat at 500 ℃ for 10h, naturally cooling and cutting off an air source to obtain the composite material; Ar/C used2H2In a mixed atmosphere, Ar and C2H2Is 90: 10.
Experimental example 1
XRD (X-ray diffraction) tests were performed on the carbon composite ternary cathode materials of example 1 and comparative example 2, and the high-nickel ternary cathode material of comparative example 1, respectively, and the test results are shown in fig. 2 and fig. 3. As can be seen from fig. 2, the crystal structure of the host material did not change significantly before and after the reaction of the high nickel ternary positive electrode material of example 1, and as can be seen from fig. 3, the crystal structure of the host material did change significantly before and after the reaction of the high nickel ternary positive electrode material of comparative example 2. Therefore, the temperature cannot be too high when growing the carbon nanotubes on the surface of the high-nickel ternary cathode material.
Experimental example 2
The carbon composite high-nickel ternary cathode materials in the embodiments 1 to 6 and the high-nickel ternary cathode material in the comparative example 1 are assembled into button cells A1, A2, A3, A4, A5, A6 and B respectively, and then the button cells are subjected to electrochemical test and rate performance test.
For button cells A1-A6, only adding a binder and a solvent into the adopted carbon composite ternary positive electrode material, then stirring and mixing the slurry, coating the prepared slurry on an aluminum foil, and drying and rolling to obtain a positive electrode plate. For the button cell B, adding the carbon nano tube, the binder and the solvent into the high-nickel ternary positive electrode material, stirring and mixing slurry, coating the obtained slurry on an aluminum foil, and drying and rolling to obtain the positive electrode plate.
The results of testing the carbon content in the positive electrode slurry prepared by using examples 1 to 6 and comparative example 1 as the positive electrode material are shown in table 1:
TABLE 1 comparison of carbon nanotube content (mass%) in slurries of examples and comparative examples
Figure BDA0001584969140000091
The binder used in the assembly process of the button cell is polyvinylidene fluoride (PVDF), the solvent used in the assembly process of the button cell is N-methyl pyrrolidone (NMP), and the electrolyte used in the assembly process of the button cell is LiPF6EC + DEC (volume ratio of EC to DEC of 1:1, LiPF61mol/L), a metal lithium sheet is used as a counter electrode, a diaphragm is a polyethylene and polypropylene composite membrane, the assembly is carried out in a glove box filled with argon (the oxygen content and the water content are both lower than 1.0ppm), and the performance of the assembled button cell is evaluated by a blue test system. When the electrochemical performance is tested, the charge-discharge voltage range of the button cell is 3.0-4.3V, the charge-discharge multiplying power is 0.1C, and the test results are shown in Table 2.
TABLE 2 comparative performance of the examples and comparative examples
Figure BDA0001584969140000092
When the multiplying power of the button cell is tested, the charging and discharging voltage range is 3.0-4.3V, and the charging and discharging multiplying power and the result are shown in a table 3.
TABLE 3 comparison of Rate test Performance of examples and comparative examples
Figure BDA0001584969140000093
Figure BDA0001584969140000101
As can be seen from Table 1, at a certain temperature, the length of the reaction time can effectively affect the content of the carbon nanotubes in the product. As can be seen from table 2, when the content of carbon nanotubes in the positive electrode slurry is the same, the electrochemical properties, including the first discharge capacity, the rate capability, etc., of the button cell using the carbon composite ternary positive electrode material of the example are superior to those of the button cell prepared by simple physical mixing in comparative example 1. As can be seen from table 3, in example 3, the carbon composite ternary cathode material has a long reaction time and a large number of coated carbon nanotubes, which affects the performance of capacity performance of the material as a whole, but the rate performance is very superior.
According to the preparation method of the carbon composite ternary cathode material for the lithium ion battery, provided by the invention, in a high-nickel ternary system, a carbon source gas is firstly adopted for pyrolysis to generate the carbon nano tube and the carbon nano tube is deposited on the surface of the material in situ to obtain the carbon composite ternary cathode material, the step of adding a conductive additive is omitted in the slurry mixing process of cathode slurry of the synthesized cathode active material, the slurry mixing process is greatly simplified, the carbon nano tube can be dispersed more uniformly by using the preparation method, the carbon nano tube can be in closer contact with the cathode material, the contact resistance is reduced, the uniformity of the slurry in the slurry mixing process of the material is well ensured, and the performance of the active material in the charging and discharging process of the material can be better exerted. Meanwhile, the electron conductivity of the whole pole piece can be effectively enhanced by compounding the in-situ carbon nano tube, the internal resistance of the battery is reduced, and the rate capability of the battery is improved. The preparation method of the carbon composite ternary cathode material is simple and reliable, and is easy for large-scale production.

Claims (10)

1. The application of the high-nickel ternary cathode material as a catalyst in the aspect of preparing the carbon nano tube is characterized in that: the method comprises the following steps: placing the high-nickel ternary positive electrode material in a reaction atmosphere, and keeping the temperature at 300-490 ℃ for 0.5-20 h; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
2. The application of the high-nickel ternary cathode material as a catalyst in the preparation of carbon nanotubes, which is characterized in that: the carbon source gas is at least one of methane, ethane, acetylene and propyne.
3. The application of the high-nickel ternary cathode material as a catalyst in the preparation of carbon nanotubes, which is characterized in that: the particle size D of the high-nickel ternary cathode material501 to 20 μm.
4. The application of the high-nickel ternary cathode material as a catalyst in the preparation of carbon nanotubes, which is characterized in that: the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
5. A carbon composite ternary cathode material is characterized in that: the preparation method of the carbon composite ternary cathode material comprises the following steps: placing the high-nickel ternary positive electrode material in a reaction atmosphere, and keeping the temperature of the high-nickel ternary positive electrode material at 300-490 ℃ for 0.5-20 hCooling to obtain the product; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
6. The carbon composite ternary positive electrode material according to claim 5, characterized in that: the mass of the carbon nano tube is 1-20% of the mass of the carbon composite ternary cathode material.
7. The carbon composite ternary positive electrode material according to claim 5, characterized in that: the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
8. The preparation method of the carbon composite ternary cathode material is characterized by comprising the following steps of: placing the high-nickel ternary positive electrode material in a reaction atmosphere, keeping the temperature of the high-nickel ternary positive electrode material at 300-490 ℃ for 0.5-20 hours, and cooling to obtain the high-nickel ternary positive electrode material; the reaction atmosphere comprises a carbon source gas; the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than 0.6 and less than 1, b is more than 0 and less than 0.3, a + b is less than 1, x is more than 0.6 and less than 1, y is more than 0 and less than 0.3, and x + y is less than 1.
9. The method for producing a carbon composite ternary positive electrode material according to claim 8, characterized in that: the high-nickel ternary positive electrode material is LiNiaCobMn1-a-bO2、LiNixCoyAl1-x-yO2At least one of; wherein a is more than or equal to 0.8 and less than or equal to 0.82, b is more than or equal to 0.1 and less than or equal to 0.12, a + b is less than or equal to 1, x is more than or equal to 0.8 and less than or equal to 0.82, y is more than or equal to 0.1 and less than or equal to 0.12, and x + y is less than or equal to 1.
10. A lithium battery using the carbon composite ternary positive electrode material as claimed in claim 5.
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