CN109256537B - Modified nickel-cobalt-aluminum ternary cathode material and preparation method thereof - Google Patents

Modified nickel-cobalt-aluminum ternary cathode material and preparation method thereof Download PDF

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CN109256537B
CN109256537B CN201810880918.8A CN201810880918A CN109256537B CN 109256537 B CN109256537 B CN 109256537B CN 201810880918 A CN201810880918 A CN 201810880918A CN 109256537 B CN109256537 B CN 109256537B
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cobalt
nickel
cathode material
aluminum ternary
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何小毛
刘佩
吴奎辰
朱玉巧
权学军
吴清国
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Zhejiang Jinying Wali New Energy 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
    • 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
    • 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 provides a preparation method of a modified nickel-cobalt-aluminum ternary cathode material, which comprises the following steps: firstly), preparing a nickel-cobalt-aluminum ternary cathode material, and secondly) preparing a titanium-doped fluorinated graphene and tetrabutylammonium hexafluorophosphate co-modified nickel-cobalt-aluminum ternary cathode material. The invention also discloses a modified nickel-cobalt-aluminum ternary cathode material prepared by the preparation method of the modified nickel-cobalt-aluminum ternary cathode material and a lithium ion battery using the modified nickel-cobalt-aluminum ternary cathode material as a cathode material. Compared with the traditional nickel-cobalt-aluminum ternary cathode material in the prior art, the modified nickel-cobalt-aluminum ternary cathode material prepared by the invention has the advantages of lower production cost, higher gram capacity, higher cycling stability, higher energy density and stacking density, and good conductivity, and avoids capacity attenuation caused by the dissolution of metal Ni, Co and Al in electrolyte directly caused by active substances and electrolyte. The cycle life is longer, and the use is safer and more stable.

Description

Modified nickel-cobalt-aluminum ternary cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a modified nickel-cobalt-aluminum ternary anode material and a preparation method thereof.
Background
With the increasing exhaustion of fossil energy, energy problems become a focus of attention. Countries in the world are continuously seeking cleaner and more environment-friendly green energy. The lithium battery has the advantages of high energy density, high voltage, long cycle life, low self-discharge rate, no memory effect, stable discharge voltage, quick charge and discharge, environmental protection and the like, is widely applied to the fields of mobile phones, portable computers, cameras, video cameras, electric vehicles and the like, and provides higher requirements on the energy density, the rate capability and the cycle life of the lithium ion battery along with the continuous expansion of the application field.
The lithium ion battery comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte, a current collector and the like. Among them, the positive electrode material largely determines the performance of the battery. The positive electrode materials that have been successfully commercialized include lithium cobaltate, lithium manganate, lithium iron phosphate, and the like. However, these positive electrode materials have their own disadvantages and drawbacks. The nickel-cobalt-aluminum ternary cathode material has the advantages of high discharge capacitance, good reaction reversibility, strong heavy current discharge capacity, good cycling stability and safety performance, properly widened charge-discharge voltage range, no safety problem or unstable structure imagination caused by overcharge, low toxicity and the like, and is a hotspot of current research. However, research finds that the nickel-cobalt-aluminum ternary positive electrode material has the defect of poor high-temperature cycle performance, and active substances are in contact with the electrolyte and can be corroded by hydrofluoric acid under a high-temperature condition to damage an interface structure, so that metal Ni, Co and Al are dissolved in the electrolyte to cause capacity attenuation.
At present, the nickel-cobalt-aluminum ternary cathode material is prepared mainly by a coprecipitation method and a solid-phase sintering method, and the material synthesized by the method has high alkalinity and is easy to absorb moisture and carbon dioxide, so that the rate capability and the cycle life of the nickel-cobalt-aluminum ternary cathode material are not influenced greatly, and the market demand and industrial production are difficult to meet.
Therefore, the development of the nickel-cobalt-aluminum ternary cathode material which is low in production cost, good in high-temperature cycle performance, stable in structure and safe to use is imperative.
Disclosure of Invention
The invention mainly aims to provide a modified nickel-cobalt-aluminum ternary cathode material and a preparation method thereof, wherein the preparation method is simple and easy to implement, has low requirements on equipment and reaction conditions, easily-obtained raw materials and low price, and compared with the traditional nickel-cobalt-aluminum ternary cathode material in the prior art, the prepared modified nickel-cobalt-aluminum ternary cathode material has the advantages of lower production cost, higher gram capacity, cycling stability, energy density and stacking density and good conductivity, and avoids the occurrence of capacity attenuation caused by the dissolution of metal Ni, Co and Al in electrolyte directly caused by active substances and the electrolyte. The cycle life is longer, and the use is safer and more stable.
In order to achieve the above purpose, the invention provides a preparation method of a modified nickel-cobalt-aluminum ternary cathode material, which comprises the following steps:
1) adding cobalt salt, lithium salt, nickel salt and aluminum nitrate into citric acid to prepare 4-5 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 10-11, and performing spray drying on the solution to finally obtain precursor particles which are uniformly mixed on a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving the heat for 3-5 hours at 500-550 ℃, then heating to 700-800 ℃, sintering for 12-15 hours, naturally cooling to room temperature, grinding the product, and sieving with a 200-mesh 400-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material;
2) dispersing fluorinated graphene and 3-chloropropylmethyldimethoxysilane in ethanol, stirring for 1-2 hours, adding tetra (dimethylamino) titanium, stirring for reacting for 4-6 hours at 40-60 ℃, filtering, and drying for 12-15 hours in a vacuum drying oven at 70-80 ℃ to obtain titanium-doped fluorinated graphene;
3) mixing and grinding the nickel-cobalt-aluminum ternary cathode material prepared in the step 1), the titanium-doped fluorinated graphene prepared in the step 2) and tetrabutylammonium hexafluorophosphate for 30-60 minutes, heating to 550-600 ℃ at a heating rate of 5-10 ℃/min in a nitrogen atmosphere, preserving heat for 6-8 hours, naturally cooling, crushing and sieving with a 200-mesh sieve to obtain the modified nickel-cobalt-aluminum ternary cathode material.
Preferably, the molar ratio of the cobalt salt, the lithium salt, the nickel salt and the aluminum nitrate in the step 1) is 0.3:2:1.7: 0.04.
Further, the cobalt salt is soluble cobalt salt, preferably cobalt sulfate, cobalt nitrate or cobalt chloride; the lithium salt is preferably lithium acetate, lithium oxalate or lithium carbonate; the nickel salt is preferably one or more of nickel citrate, nickel nitrate, nickel chloride, nickel acetate or nickel carbonate.
Preferably, the mass ratio of the fluorinated graphene, the 3-chloropropylmethyldimethoxysilane, the ethanol and the tetra (dimethylamino) titanium in the step 2) is (2-3):0.1, (5-10): 0.1-0.3.
Preferably, the mass ratio of the nickel-cobalt-aluminum ternary positive electrode material, the titanium-doped fluorinated graphene and the tetrabutylammonium hexafluorophosphate in the step 3) is (1-2): 0.01-0.03): 0.005.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) the preparation method of the modified nickel-cobalt-aluminum ternary cathode material disclosed by the invention is simple and feasible, has low requirements on equipment and reaction conditions, is easy to obtain raw materials, is low in price and is suitable for large-scale production.
(2) Compared with the traditional nickel-cobalt-aluminum ternary cathode material in the prior art, the modified nickel-cobalt-aluminum ternary cathode material disclosed by the invention has the advantages of lower production cost, higher gram capacity, higher cycling stability, higher energy density and stacking density, and good conductivity, and avoids capacity attenuation caused by the dissolution of metal Ni, Co and Al in electrolyte directly caused by active substances and electrolyte. The cycle life is longer, and the use is safer and more stable.
(3) The modified nickel-cobalt-aluminum ternary cathode material disclosed by the invention has the advantages that the Ni-Co-Li-Al precursor is prepared firstly, and the titanium-doped fluorinated graphene is coated on the surface of the material, so that the stability and the electrochemical performance of the cathode material are improved, the cathode material has higher energy density, stability and cycle service life, the dissolution of hydrofluoric acid to transition metal can be reduced, the increase of electron transfer impedance in the cycle process can be prevented, the surface structure of the stable material in the charge and discharge process can be ensured, and the electrochemical performance of the material can be improved.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
The fluorinated graphene used in the examples of the present invention was purchased from Nanjing Xiancheng nanomaterial science and technology Co., Ltd, and the other raw materials were purchased from Mobei (Shanghai) Biotechnology Co., Ltd.
Example 1
A preparation method of a modified nickel-cobalt-aluminum ternary cathode material comprises the following steps:
1) adding cobalt sulfate, nickel citrate, lithium acetate and aluminum nitrate into citric acid to prepare 4 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 10, and performing spray drying on the solution to finally obtain precursor particles uniformly mixed at a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving heat for 3 hours at 500 ℃, heating to 700 ℃, sintering for 12 hours, naturally cooling to room temperature, grinding the product, and sieving with a 200-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt sulfate to the nickel citrate to the lithium acetate to the aluminum nitrate is 0.3:2:1.7: 0.04;
2) dispersing 20g of fluorinated graphene and 1g of 3-chloropropylmethyldimethoxysilane in 50g of ethanol, stirring for 1 hour, adding 1g of tetra (dimethylamino) titanium, stirring for reacting for 4 hours at 40 ℃, filtering, and drying in a vacuum drying oven at 70 ℃ for 12 hours to obtain titanium-doped fluorinated graphene;
3) 10g of the nickel-cobalt-aluminum ternary positive electrode material prepared in the step 1), 0.1g of titanium-doped fluorinated graphene prepared in the step 2) and 0.05g of tetrabutylammonium hexafluorophosphate are mixed and milled for 30 minutes, the temperature is increased to 550 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 6 hours, the mixture is naturally cooled, and the mixture is crushed and sieved by a 200-mesh sieve, so that the modified nickel-cobalt-aluminum ternary positive electrode material is obtained.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Example 2
A preparation method of a modified nickel-cobalt-aluminum ternary cathode material comprises the following steps:
1) adding cobalt nitrate, lithium carbonate, nickel acetate and aluminum nitrate into citric acid to prepare 4.3 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 11, and performing spray drying on the solution to finally obtain precursor particles uniformly mixed at a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving heat for 3.5 hours at 510 ℃, heating to 730 ℃, sintering for 13 hours, naturally cooling to room temperature, grinding the product, and sieving with a 250-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt nitrate to the lithium carbonate to the nickel acetate to the aluminum nitrate is 0.3:2:1.7: 0.04.
2) Dispersing 23g of fluorinated graphene and 1g of 3-chloropropylmethyldimethoxysilane in 65g of ethanol, stirring for 1.2 hours, adding 1.5g of tetrakis (dimethylamino) titanium, stirring and reacting at 45 ℃ for 4.5 hours, filtering, and drying in a vacuum drying oven at 73 ℃ for 13 hours to obtain titanium-doped fluorinated graphene;
3) 13g of the nickel-cobalt-aluminum ternary positive electrode material prepared in the step 1), 0.15g of titanium-doped fluorinated graphene prepared in the step 2) and 0.05g of tetrabutylammonium hexafluorophosphate are mixed and milled for 40 minutes, the temperature is increased to 570 ℃ at the heating rate of 7 ℃/min under the nitrogen atmosphere, the temperature is kept for 6.5 hours, the mixture is naturally cooled, and the mixture is crushed and sieved by a 200-mesh sieve, so that the modified nickel-cobalt-aluminum ternary positive electrode material is obtained.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Example 3
A preparation method of a modified nickel-cobalt-aluminum ternary cathode material comprises the following steps:
1) adding cobalt chloride, lithium oxalate, nickel chloride and aluminum nitrate into citric acid to prepare 4.5 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 10, and performing spray drying on the solution to finally obtain precursor particles uniformly mixed at a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving heat for 4 hours at 535 ℃, heating to 750 ℃, sintering for 13.5 hours, naturally cooling to room temperature, grinding the product, and sieving with a 300-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt chloride to the lithium oxalate to the nickel chloride to the aluminum nitrate is 0.3:2:1.7: 0.04.
2) Dispersing 26g of fluorinated graphene and 1g of 3-chloropropylmethyldimethoxysilane in 85g of ethanol, stirring for 1.5 hours, adding 2g of tetra (dimethylamino) titanium, stirring and reacting at 50 ℃ for 5 hours, filtering, and drying in a vacuum drying oven at 76 ℃ for 13.5 hours to obtain titanium-doped fluorinated graphene;
3) mixing and grinding 15g of the nickel-cobalt-aluminum ternary positive electrode material prepared in the step 1), 0.2g of titanium-doped fluorinated graphene prepared in the step 2) and 0.05g of tetrabutylammonium hexafluorophosphate for 50 minutes, heating to 580 ℃ at a heating rate of 8 ℃/min in a nitrogen atmosphere, preserving heat for 7 hours, naturally cooling, crushing and sieving with a 200-mesh sieve to obtain the modified nickel-cobalt-aluminum ternary positive electrode material.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Example 4
A preparation method of a modified nickel-cobalt-aluminum ternary cathode material comprises the following steps:
1) adding cobalt salt, lithium salt, nickel salt and aluminum nitrate into citric acid to prepare 5 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 11, and performing spray drying on the solution to finally obtain precursor particles uniformly mixed at a molecular level; putting the precursor into an atmosphere furnaceIntroducing oxygen, preserving heat for 4.5 hours at 545 ℃, heating to 780 ℃, sintering for 14.5 hours, naturally cooling to room temperature, grinding the product, and sieving with a 350-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt salt, the lithium salt, the nickel salt and the aluminum nitrate is 0.3:2:1.7: 0.04; the cobalt salt is formed by mixing cobalt sulfate, cobalt nitrate and cobalt chloride according to the mass ratio of 1:2: 3; the lithium salt is formed by mixing lithium acetate, lithium oxalate and lithium carbonate according to the mass ratio of 2:3:1 and the mass ratio of 2:3: 3; the nickel salt is formed by mixing nickel citrate, nickel nitrate and nickel chloride according to the mass ratio of 3:4: 5;
2) dispersing 28g of fluorinated graphene and 1g of 3-chloropropylmethyldimethoxysilane in 85g of ethanol, stirring for 1.7 hours, adding 2.5g of tetra (dimethylamino) titanium, stirring for reaction for 5.5 hours at 57 ℃, filtering, and drying in a vacuum drying oven at 78 ℃ for 14.5 hours to obtain titanium-doped fluorinated graphene;
3) mixing and grinding 18g of the nickel-cobalt-aluminum ternary cathode material prepared in the step 1), 0.25g of titanium-doped fluorinated graphene prepared in the step 2) and 0.05g of tetrabutylammonium hexafluorophosphate for 55 minutes, heating to 590 ℃ at a heating rate of 9 ℃/min in a nitrogen atmosphere, preserving heat for 7.5 hours, naturally cooling, crushing and sieving with a 200-mesh sieve to obtain the modified nickel-cobalt-aluminum ternary cathode material.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Example 5
A preparation method of a modified nickel-cobalt-aluminum ternary cathode material comprises the following steps:
1) adding cobalt nitrate, lithium acetate, nickel citrate and aluminum nitrate into citric acid to prepare 5 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 11, and performing spray drying on the solution to finally obtain precursor particles uniformly mixed at a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving the heat for 5 hours at 550 ℃, and then heating to 800 ℃ for sintering for 15 hoursNaturally cooling to room temperature, grinding the product, and sieving with a 400-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt nitrate to the lithium acetate to the nickel citrate to the aluminum nitrate is 0.3:2:1.7: 0.04.
2) Dispersing 30g of fluorinated graphene and 1g of 3-chloropropylmethyldimethoxysilane in 100g of ethanol, stirring for 2 hours, adding 3g of tetra (dimethylamino) titanium, stirring and reacting at 60 ℃ for 6 hours, filtering, and drying in a vacuum drying oven at 80 ℃ for 15 hours to obtain titanium-doped fluorinated graphene;
3) 20g of the nickel-cobalt-aluminum ternary positive electrode material prepared in the step 1), 0.3g of titanium-doped fluorinated graphene prepared in the step 2) and 0.05g of tetrabutylammonium hexafluorophosphate are mixed and milled for 60 minutes, the temperature is increased to 600 ℃ at the heating rate of 10 ℃/min in the nitrogen atmosphere, the temperature is kept for 8 hours, the mixture is naturally cooled, and the mixture is crushed and sieved by a 200-mesh sieve, so that the modified nickel-cobalt-aluminum ternary positive electrode material is obtained.
A modified nickel-cobalt-aluminum ternary cathode material is prepared by adopting the preparation method of the modified nickel-cobalt-aluminum ternary cathode material.
A lithium ion battery adopts the modified nickel-cobalt-aluminum ternary cathode material as a cathode material.
Comparative example
The present example provides a nickel-cobalt-aluminum ternary cathode material, which has the same raw materials and formula as in example 1 of chinese patent CN 104900869B.
The nickel-cobalt-manganese ternary positive electrode materials obtained in the above examples 1 to 5 and comparative example were subjected to the relevant performance tests, and the test results are shown in table 1, and the test methods are as follows: dissolving the lithium manganate positive electrode material, Super P and PVDF in a mass ratio of 8:1:1 in N-methyl pyrrolidone (NMP) to prepare slurry, and coating the slurry on an aluminum foil by using an automatic coating machine. After vacuum drying for 12h, cutting into positive plates. The obtained product is transferred into a glove box with argon atmosphere, and a 2032 button cell is assembled by a metal lithium sheet, a diaphragm, electrolyte and a liquid absorption film. Wherein the electrolyte is 1mol L-1LiPF6EC/DMC (volume ratio 1:1), septum Celgard 2400. And (3) carrying out charge and discharge tests on the assembled button cell by adopting a LAND test system, wherein the cut-off voltage of the test is 3-4.3V.Cyclic voltammetry and ac impedance tests were performed at the CHI660C electrochemical workstation.
TABLE 1
Figure GDA0002998573370000061
As can be seen from table 1, the modified nickel-cobalt-aluminum ternary cathode material disclosed in the embodiment of the present invention has more excellent electrochemical properties than cathode materials in the prior art.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (6)

1. The preparation method of the modified nickel-cobalt-aluminum ternary cathode material is characterized by comprising the following steps of:
1) adding cobalt salt, lithium salt, nickel salt and aluminum nitrate into citric acid to prepare 4-5 mol.L-1Adding ammonia water into the mixed salt solution, adjusting the pH value of the solution to 10-11, and performing spray drying on the solution to finally obtain precursor particles which are uniformly mixed on a molecular level; introducing oxygen into the precursor in an atmosphere furnace, preserving the heat for 3-5 hours at 500-550 ℃, then heating to 700-800 ℃, sintering for 12-15 hours, naturally cooling to room temperature, grinding the product, and sieving with a 200-mesh 400-mesh sieve to obtain the nickel-cobalt-aluminum ternary cathode material; the molar ratio of the cobalt salt, the lithium salt, the nickel salt and the aluminum nitrate is 0.3:2:1.7: 0.04;
2) dispersing fluorinated graphene and 3-chloropropylmethyldimethoxysilane in ethanol, stirring for 1-2 hours, adding tetra (dimethylamino) titanium, stirring for reacting for 4-6 hours at 40-60 ℃, filtering, and drying for 12-15 hours in a vacuum drying oven at 70-80 ℃ to obtain titanium-doped fluorinated graphene; the mass ratio of the fluorinated graphene to the 3-chloropropylmethyldimethoxysilane to the ethanol to the tetra (dimethylamino) titanium is (2-3) to (0.1), (5-10) to (0.1-0.3);
3) mixing and grinding the nickel-cobalt-aluminum ternary positive electrode material prepared in the step 1), the titanium-doped fluorinated graphene prepared in the step 2) and tetrabutylammonium hexafluorophosphate for 30-60 minutes, heating to 550-600 ℃ at a heating rate of 5-10 ℃/min in a nitrogen atmosphere, preserving heat for 6-8 hours, naturally cooling, crushing and sieving with a 200-mesh sieve to obtain a modified nickel-cobalt-aluminum ternary positive electrode material; the mass ratio of the nickel-cobalt-aluminum ternary positive electrode material, the titanium-doped fluorinated graphene and the tetrabutylammonium hexafluorophosphate is (1-2): 0.01-0.03): 0.005.
2. The preparation method of the modified nickel-cobalt-aluminum ternary cathode material as claimed in claim 1, wherein the cobalt salt is cobalt sulfate, cobalt nitrate or cobalt chloride.
3. The method for preparing the modified nickel-cobalt-aluminum ternary cathode material as claimed in claim 1, wherein the lithium salt is lithium acetate, lithium oxalate or lithium carbonate.
4. The preparation method of the modified nickel-cobalt-aluminum ternary cathode material as claimed in claim 1, wherein the nickel salt is one or more of nickel citrate, nickel nitrate, nickel chloride, nickel acetate or nickel carbonate.
5. The modified nickel-cobalt-aluminum ternary cathode material prepared by the preparation method of the modified nickel-cobalt-aluminum ternary cathode material according to any one of claims 1 to 4.
6. A lithium ion battery adopting the modified nickel-cobalt-aluminum ternary cathode material as claimed in claim 5 as a cathode material.
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Citations (4)

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CN106957055A (en) * 2017-02-27 2017-07-18 华南师范大学 A kind of sulphur, nitrogen, transient metal doped graphene and preparation method and application
CN107935059A (en) * 2017-11-17 2018-04-20 中钢集团安徽天源科技股份有限公司 A kind of nickel cobalt aluminium ternary material precursor and preparation method thereof
CN107994219A (en) * 2017-11-27 2018-05-04 桑顿新能源科技有限公司 A kind of metal-doped composite positive pole of graphene coated and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104538620A (en) * 2014-12-28 2015-04-22 王帅 Preparation method of fluorinated graphene coated manganese, cobalt and lithium positive electrode material
CN106957055A (en) * 2017-02-27 2017-07-18 华南师范大学 A kind of sulphur, nitrogen, transient metal doped graphene and preparation method and application
CN107935059A (en) * 2017-11-17 2018-04-20 中钢集团安徽天源科技股份有限公司 A kind of nickel cobalt aluminium ternary material precursor and preparation method thereof
CN107994219A (en) * 2017-11-27 2018-05-04 桑顿新能源科技有限公司 A kind of metal-doped composite positive pole of graphene coated and preparation method thereof

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