CN113745484A - Modified ternary lithium ion battery positive electrode material and preparation method and application thereof - Google Patents

Modified ternary lithium ion battery positive electrode material and preparation method and application thereof Download PDF

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CN113745484A
CN113745484A CN202111045232.5A CN202111045232A CN113745484A CN 113745484 A CN113745484 A CN 113745484A CN 202111045232 A CN202111045232 A CN 202111045232A CN 113745484 A CN113745484 A CN 113745484A
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nickel
cobalt
lithium ion
ion battery
manganese
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李璐纯
赵尧敏
崔铁兵
李英华
王红芳
李慧
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Zhongyuan University of Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 belongs to the technical field of lithium ion battery materials, and discloses a modified ternary lithium ion battery positive electrode material and a preparation method and application thereof, wherein the modified ternary lithium ion battery positive electrode is of a core-shell structure, an inner core of the modified ternary lithium ion battery positive electrode is a first nickel-cobalt-manganese ternary material, an outer shell of the modified ternary lithium ion battery positive electrode is a second nickel-cobalt-manganese ternary material, and the mass ratio of the outer shell to the inner core is 1: 8-10; wherein the molar ratio of Ni to Co to Mn in the first nickel-cobalt-manganese ternary material is 13-15: 2-4; the molar ratio of Ni to Co to Mn in the second nickel-cobalt-manganese ternary material is 0.5-2: 1:1, and lithium ions are doped in the second nickel-cobalt-manganese ternary material. The nickel-cobalt-manganese ternary cathode material prepared by the method has high specific capacity, excellent rate property and excellent processing performance, and simultaneously can reduce the price of the cathode material and the battery price due to the reduction of the cobalt content.

Description

Modified ternary lithium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a modified ternary lithium ion battery positive electrode material and a preparation method and application thereof.
Background
As an important strategic industry in China, the popularization of new energy automobiles has important significance for improving the energy consumption structure in China and reducing the external dependence of petroleum. China has the largest market of pure electric vehicles in the world and also has the largest production capacity of the pure electric vehicles in the world.
The power battery of the electric automobile is a core component of the pure electric automobile. Lithium ion batteries are the youngest high energy batteries and are the batteries with the best overall electrochemical performance of all the chemical power sources commercialized at present. The positive electrode active material is the most costly component of the lithium ion battery matrix, accounting for about 40%.
At present, four types of lithium ion battery positive electrode materials are commercialized, namely, a lithium cobaltate, lithium manganate, lithium iron phosphate and a nickel-cobalt-manganese ternary positive electrode, wherein in the field of large power batteries (such as passenger vehicles in pure electric vehicles), the cobalt price is frequently innovative, and the nickel-cobalt-manganese ternary material becomes the mainstream of the global power battery market due to the fact that the nickel-cobalt-manganese ternary material has high energy density, long cycle life, lower cost and excellent rate property.
In the nickel-cobalt-manganese ternary cathode material, the influence of the nickel content on the performance of the material is very important. Low-nickel ternary materials such as NCM333 were first commercialized due to their superior rate properties, safety, cycle stability and processability, but the low-nickel ternary materials still have a high cobalt content and thus a high cost, and due to their low nickel content, they have a low energy density and thus cannot meet the increasing mileage requirements of passenger vehicles.
In the nickel-cobalt-manganese ternary material, along with the increase of the content of nickel, the specific capacity and the energy density of the battery which can be exerted are improved, but the rate property, the safety performance and the processability are all deteriorated.
In order to solve the problems in the prior art, the invention provides a modified ternary lithium ion battery positive electrode material and a preparation method and application thereof.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a modified ternary lithium ion battery positive electrode material, a preparation method and application thereof, the invention utilizes a field coating method to prepare the ternary positive electrode material which takes 'high nickel' as a core and 'low nickel' as a shell and has a core-shell structure by accurately controlling precipitation parameters, and adopts anion and cation double doping modification in a lithium preparation stage, so that the prepared nickel-cobalt-manganese ternary positive electrode material has high specific capacity, excellent rate property and excellent processing performance, meanwhile, the cobalt content is reduced, the price of the positive electrode material and the price of the battery are reduced, and the problems that the pure high nickel ternary positive electrode material has poor rate property, cannot bear charge and discharge, the capacity is difficult to exert large current, the processing technology requirement is harsh and the like are solved.
The invention relates to a modified ternary lithium ion battery anode material, a preparation method and application thereof, which are realized by the following technical scheme:
the first purpose of the invention is to provide a modified ternary lithium ion battery anode material, wherein the modified ternary lithium ion battery anode is of a core-shell structure, an inner core of the modified ternary lithium ion battery anode material is a first nickel-cobalt-manganese ternary material, an outer shell of the modified ternary lithium ion battery anode material is a second nickel-cobalt-manganese ternary material, and the mass ratio of the outer shell to the inner core is 1: 8-10;
lithium ions are doped in the second nickel-cobalt-manganese ternary material;
wherein the molar ratio of Ni to Co to Mn in the first nickel-cobalt-manganese ternary material is 13-15: 2-4;
the molar ratio of Ni to Co to Mn in the second nickel-cobalt-manganese ternary material is 0.5-2: 1: 1.
Further, the second nickel-cobalt-manganese ternary material is doped with halogen and metal elements;
the halogen is any one of F, Cl, Br and I;
the metal element is one or more of Ti and Mg;
the molar ratio of the total amount of the halogen and the metal element to the total amount of the first nickel-cobalt-manganese ternary material and the second nickel-cobalt-manganese ternary material is 0.5-2%.
Further, the halogen and the metal element are mixed in equimolar amounts.
The second purpose of the invention is to provide a preparation method of the modified ternary lithium ion battery anode material, which comprises the following steps:
s1, preparing a core material:
uniformly dispersing nickel salt, cobalt salt and manganese salt in a water solvent to prepare a first mixed salt solution, adding a precipitator A and a complexing agent A into the first mixed salt solution, then precipitating the first mixed salt solution for 5-7 hours at 50-60 ℃ and under the condition that the pH value is 10.5-11.5 in an inert atmosphere, and then performing primary aging for 7-9 hours to obtain an inner core material;
s2, preparing a precursor of the modified ternary lithium ion battery anode material:
uniformly dispersing nickel salt, cobalt salt and manganese salt in a water solvent to prepare a second mixed salt solution, simultaneously adding the second mixed salt solution, a precipitator B and a complexing agent B into the obtained core material in an inert atmosphere, precipitating for 2-6 h under the conditions of 50-60 ℃ and pH of 10-11, then performing secondary aging for 7-9 h, and coating a layer of core material on the surface of the core material to obtain a modified ternary lithium ion battery anode material precursor;
s3, uniformly mixing the precursor of the modified ternary lithium ion battery positive electrode material with the doping elements by wet ball milling, and then carrying out sectional calcination on the mixture in an oxygen atmosphere to obtain the modified ternary lithium ion battery positive electrode material;
the doping element is a lithium source, or a lithium source, halogen and a metal element.
Further, the wet ball milling is carried out in an organic solvent, the ball milling rotating speed is 200-400 r/min, and the ball milling time is 2-4 h.
Further, the step-by-step calcination is to calcine at 500-600 ℃ for 4-6 h, at 800-850 ℃ for 12-18 h, and at 850-950 ℃ for 0.5-2 h.
Further, in the first mixed salt solution, the dosage ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the water solvent is 1-3 mol/L;
the molar ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the precipitant A is 1: 1-3;
the molar ratio of the precipitant A to the complexing agent A is 3-5: 1.
Further, in the second mixed salt solution, the dosage ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the water solvent is 1-3 mol/L;
the molar ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the precipitant B is 1: 1-3;
the molar ratio of the precipitant B to the complexing agent B is 3-5: 1.
Further, the precipitant A or the precipitant B is one or two of sodium hydroxide and potassium hydroxide;
and the complexing agent A or the complexing agent B is ammonia water.
The third purpose of the invention is to provide the application of the modified ternary lithium ion battery cathode material in the preparation of lithium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through the innovation of a nickel-cobalt-manganese ternary precursor structure (the structure of high nickel is used as a core, the structure of low nickel is used as a shell and a core-shell structure), and the anion and cation double doping modification is simultaneously carried out in the lithium preparation stage, so that the prepared nickel-cobalt-manganese ternary positive electrode material has the high specific capacity of the high nickel ternary positive electrode material, and also has the excellent rate property and processing property of the low nickel ternary positive electrode material, and the exertion of the capacity of the high nickel core and the rate property are further improved through the anion and cation double doping modification.
The nickel-cobalt-manganese ternary cathode material with a core-shell structure and high nickel as a core and low nickel as a shell can be prepared by utilizing the same nickel-cobalt-manganese ternary material reaction kettle and modulating the deposition parameters on site in the codeposition stage, and the prepared material has the advantages of lower material cost, and more excellent battery performance and processing performance.
In order to comprehensively utilize the advantages of the high-nickel and low-nickel ternary materials, the invention prepares the nickel-cobalt-manganese ternary positive electrode precursor which takes high nickel as a core and low nickel as a shell and has a novel core-shell structure by regulating deposition parameters and coating on site in an original reaction kettle, and carries out dry-method anion and cation double doping modification in the lithium preparation stage, wherein the core of high nickel can provide high energy density and reduce the cobalt content, so that the material cost is reduced, the shell of low nickel can provide excellent rate property, safety and processability, and the anion and cation double doping modification further improves the exertion of the energy density of the material.
According to the invention, through structural design and deposition parameter regulation and control, the high-nickel ternary positive electrode material which has high energy density, high rate property and good processing performance is prepared, and is used for providing a power battery of a pure electric vehicle with long endurance and high rate charge-discharge function.
The invention carries out on-site coating by adjusting the deposition parameters, does not additionally increase equipment and is convenient to prepare; the prepared battery material has a novel core-shell structure, the core material adopts high nickel to underestimate low manganese, the cobalt content is reduced, the material cost is reduced, the shell material adopts low nickel and slightly higher cobalt content, and meanwhile, the performance of the energy density of the material is improved and the rate property and the processing performance of the material are improved through the dry doping of anions and cations.
Drawings
Fig. 1 is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material precursor of the present invention, wherein fig. 1(1) is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material precursor of comparative example 1; FIG. 1(2) is a scanning electron micrograph of a precursor of the modified ternary lithium ion battery positive electrode material of example 1; FIG. 1(3) is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material of comparative example 1; FIG. 1(4) is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material of example 1; FIG. 1(5) is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material of example 2; FIG. 1(6) is a scanning electron micrograph of the modified ternary lithium ion battery positive electrode material of example 3;
FIG. 2 is a cyclic voltammogram of the present invention; wherein, fig. 2(a) is a cyclic voltammetry spectrum of the modified ternary lithium ion battery positive electrode material of comparative example 1; fig. 2(B) is a cyclic voltammetry spectrum of the modified ternary lithium ion battery positive electrode material of example 1; fig. 2(B) is a cyclic voltammetry spectrum of the modified ternary lithium ion battery positive electrode material of example 2; fig. 2(D) is a cyclic voltammetry spectrum of the modified ternary lithium ion battery positive electrode material of example 3;
fig. 3 is a charge-discharge curve of the modified ternary lithium ion battery positive electrode material of example 3 at different rates.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be noted that the concentrations of nitrogen and oxygen used in the following examples are both 99.999%, and the flow rate of the gas can ensure that the nitrogen can maintain a micro-positive pressure in the reaction kettle, and the gas is stably vented from the reaction system after passing through the reaction system.
Example 1
A preparation method of a modified ternary lithium ion battery anode material comprises the following steps:
s1, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 14 to 3, mixing to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator A, a complexing agent A and a first mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle for precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 11.1, carrying out coprecipitation reaction for 6 hours, and carrying out primary aging for 8 hours to prepare a core material, namely Ni0.75Co0.15Mn0.15(OH)2。
S2, weighing nickel sulfate, cobalt sulfate and sulfur respectively according to the molar ratio of Ni, Co and Mn to 1:1:1And mixing manganese acid to obtain second mixed salt, and uniformly dispersing the second mixed salt in the deoxygenated high-purity water according to the proportion of 2moL/L to prepare a second mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator B, a complexing agent B and a second mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle in which a core material is generated to perform a second precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 10.5, performing a coprecipitation reaction for 2 hours, performing primary aging for 8 hours, and making the coating amount of a shell coated on the core material be 10%, thereby preparing a modified ternary lithium ion battery anode material precursor named as [ Ni ]0.75Co0.15Mn0.15(OH)2】·【Ni1/ 3Co1/3Mn1/3(OH)2】。
S3, filtering and washing the precursor of the modified ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor and lithium hydroxide together, and then carrying out three-stage calcination (5 h at 550 ℃, 15h at 830 ℃ and 1h at 900 ℃) in an oxygen atmosphere to obtain a ternary anode active material Li [ Ni ]0.75Co0.15Mn0.15】·【Ni1/3Co1/3Mn1/3】O2(denoted as NCM701515+ NCM 333).
In this example, the molar ratio of the precipitant a to the mixed salt is 2:1, the molar ratio of the precipitant a to the complexing agent a is 4:1, and the pH of the reaction system is controlled to be 11.1 by the feeding amounts of the precipitant a and the complexing agent a.
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of lithium ions to the total amount of nickel, cobalt and manganese in the material was 105%.
In this embodiment, the solvent for wet ball milling is acetone, the ball milling speed is 300r/min, and the ball milling time is 3 hours.
The ternary cathode active material obtained in the embodiment is used as an experimental battery to perform electrochemical performance test, and has a specific discharge capacity of 162mAh/g at a multiplying power of 0.1C, and a specific discharge capacity of 133mAh/g at a multiplying power of 5C, which is about 82.1% of that at 0.1C. The cyclic voltammogram is shown in FIG. 2 (B).
Example 2
The embodiment provides a preparation method of a modified ternary lithium ion battery anode material, which comprises the following steps:
s1, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 14 to 3, mixing to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator A, a complexing agent A and a first mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle for precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 11.1, carrying out coprecipitation reaction for 6 hours, and carrying out primary aging for 8 hours to obtain the core material, namely Ni0.75Co0.15Mn0.15(OH)2。
And S2, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 1 to 1, mixing to obtain a second mixed salt, uniformly dispersing the second mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a second mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator B, a complexing agent B and a second mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle in which a core material is generated to perform a second precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 10.5, performing a coprecipitation reaction for 2 hours, performing primary aging for 8 hours, and making the coating amount of a shell coated on the core material be 10%, thus obtaining the modified ternary lithium ion battery anode material precursor [ Ni & lt/EN & gt0.75Co0.15Mn0.15(OH)2】·【Ni1/3Co1/3Mn1/3(OH)2】。
S3, filtering and washing the precursor of the modified ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor, lithium hydroxide, titanium dioxide and ammonium fluoride together, and then carrying out three-stage calcination (5 h at 550 ℃, 15h at 830 ℃ and 1h at 900 ℃) in an oxygen atmosphere to obtain a ternary anode active material, namely Li [ Ni ]0.75Co0.15Mn0.15】·【Ni1/3Co1/3Mn1/3】O2(denoted as NCM701515+ NCM 333).
In this example, the molar ratio of the precipitant a to the mixed salt is 2:1, the molar ratio of the precipitant a to the complexing agent a is 4:1, and the pH of the reaction system is controlled to be 11.1 by the feeding amounts of the precipitant a and the complexing agent a.
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of lithium ions to the total amount of nickel, cobalt and manganese in the material was 105%.
In this example, the molar ratio of titanium dioxide and ammonium fluoride was 1:1, and the molar ratio of the total amount of titanium dioxide and ammonium fluoride to the total amount of nickel cobalt manganese in the entire material was 1%.
In this embodiment, the solvent for wet ball milling is acetone, the ball milling speed is 300r/min, and the ball milling time is 3 hours.
The ternary positive active material obtained in the embodiment is used as an experimental battery to perform electrochemical performance test, and has a specific discharge capacity of 190mAh/g at a multiplying power of 0.1C, 127mAh/g at a multiplying power of 5C and about 66.8% of that at 0.1C. The cyclic voltammogram is shown in FIG. 2 (C).
Example 3
The embodiment provides a preparation method of a modified ternary lithium ion battery anode material, which comprises the following steps:
s1, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 14 to 3, mixing to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator A, a complexing agent A and a first mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle for precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 11.1, carrying out coprecipitation reaction for 6 hours, and carrying out primary aging for 8 hours to obtain a core material Ni0.75Co0.15Mn0.15(OH)2。
S2, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 1 to 1, mixing to obtain a second mixed salt, uniformly dispersing the second mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain the final productTo a second mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator B, a complexing agent B and a second mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle in which a core material is generated to perform a second precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 10.5, performing a coprecipitation reaction for 2 hours, performing primary aging for 8 hours, and making the coating amount of a shell coated on the core material be 10%, thus obtaining the modified ternary lithium ion battery anode material precursor [ Ni & lt/EN & gt0,75Co0.15Mn0.15(OH)2】·【Ni1/3Co1/3Mn1/3(OH)2】。
S3, filtering and washing the precursor of the modified ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor, lithium hydroxide, magnesium acetate and ammonium fluoride together, and then carrying out three-stage calcination (5 h at 550 ℃, 15h at 830 ℃ and 1h at 900 ℃) in an oxygen atmosphere to obtain a ternary anode active material Li [ Ni ]0.75Co0.15Mn0.15】·【Ni1/3Co1/ 3Mn1/3】O2(NCM701515+NCM333)。
In this example, the molar ratio of the precipitant a to the mixed salt is 2:1, the molar ratio of the precipitant a to the complexing agent a is 4:1, and the pH of the reaction system is controlled to be 11.1 by the feeding amounts of the precipitant a and the complexing agent a.
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of lithium ions to the total amount of nickel, cobalt and manganese in the material was 105%.
In this example, the molar ratio of magnesium acetate and ammonium fluoride was 1:1, and the molar ratio of the total amount of magnesium acetate and ammonium fluoride to the total amount of nickel cobalt manganese in the entire material was 1%.
In this embodiment, the solvent for wet ball milling is acetone, the ball milling speed is 300r/min, and the ball milling time is 3 hours.
When the ternary cathode active material obtained in this example is used as an experimental battery to perform an electrochemical performance test, a cyclic voltammetry curve of the ternary cathode active material is shown in fig. 2(D), and a charge-discharge curve of the ternary cathode active material under different multiplying factors is shown in fig. 3, it can be seen that the specific discharge capacity is 189mAh/g at a multiplying factor of 0.1C, 135mAh/g at a multiplying factor of 5C, and is about 71.4% of that at 0.1C.
Example 4
The embodiment provides a preparation method of a modified ternary lithium ion battery anode material, which comprises the following steps:
s1, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 13 to 4 to 3, mixing to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of a high-purity nitrogen atmosphere, feeding a precipitator A, a complexing agent A and a first mixed salt solution in parallel flow at the same time, allowing the mixture to enter a reaction kettle for precipitation reaction, controlling the precipitation temperature at 50 ℃ and the pH value at 10.5, carrying out coprecipitation reaction for 5 hours, and carrying out primary aging for 7 hours to obtain the core material.
S2, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 0.5 to 1, mixing to obtain a second mixed salt, uniformly dispersing the second mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a second mixed salt solution. Under the protection of a high-purity nitrogen atmosphere, simultaneously feeding a precipitator B, a complexing agent B and a second mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle in which a core material is generated to perform a second precipitation reaction, controlling the precipitation temperature at 50 ℃ and the pH value at 10, performing a coprecipitation reaction for 4 hours, and performing primary aging for 7 hours to ensure that the coating amount of a shell coated on the core material is 12.5%, thus obtaining the modified ternary lithium ion battery anode material precursor.
And S3, filtering and washing the precursor of the modified ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor, lithium hydroxide, titanium dioxide and ammonium bromide together, and then carrying out three-stage calcination (4 h at 500 ℃, 12h at 800 ℃ and 0.5h at 850 ℃) in an oxygen atmosphere to obtain the ternary anode active material.
In this example, the molar ratio of the precipitant a to the mixed salt is 1:1, and the molar ratio of the precipitant a to the complexing agent a is 3: 1.
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of the lithium ions to the total amount of nickel, cobalt, and manganese in the material is 104%.
In this example, the molar ratio of titanium dioxide to ammonium bromide was 1:1, and the molar ratio of the total amount of titanium dioxide and ammonium bromide to the total amount of nickel cobalt manganese in the entire material was 0.5%.
In this embodiment, the solvent for wet ball milling is acetone, the ball milling speed is 200r/min, and the ball milling time is 2 hours.
Example 5
The embodiment provides a preparation method of a modified ternary lithium ion battery anode material, which comprises the following steps:
s1, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 15 to 3 to 2, mixing to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of a high-purity nitrogen atmosphere, feeding a precipitator A, a complexing agent A and a first mixed salt solution in parallel flow at the same time, allowing the mixture to enter a reaction kettle for precipitation reaction, controlling the precipitation temperature at 60 ℃ and the pH value at 11.5, carrying out coprecipitation reaction for 7 hours, and carrying out primary aging for 9 hours to obtain the core material.
S2, weighing nickel sulfate, cobalt sulfate and manganese sulfate respectively according to the molar ratio of Ni to Co to Mn of 2 to 1, mixing to obtain second mixed salt, uniformly dispersing the second mixed salt in deoxygenated high-purity water according to the ratio of 2moL/L, and preparing to obtain a second mixed salt solution. And under the protection of a high-purity nitrogen atmosphere, simultaneously feeding a precipitator B, a complexing agent B and a second mixed salt solution in a parallel flow manner, allowing the mixture to enter a reaction kettle in which a core material is generated for a second precipitation reaction, controlling the precipitation temperature to be 60 ℃ and the pH value to be 11, performing a coprecipitation reaction for 6 hours, and performing primary aging for 9 hours to ensure that the coating amount of a shell coated on the core material is 11%, thus obtaining the modified ternary lithium ion battery anode material precursor.
And S3, filtering and washing the precursor of the modified ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor, lithium hydroxide, titanium dioxide and ammonium chloride together, and then carrying out three-stage calcination (at 600 ℃ for 6h, 850 ℃ for 18h and 950 ℃ for 2h) in an oxygen atmosphere to obtain the ternary anode active material.
In this example, the molar ratio of the precipitant a to the mixed salt is 3:1, and the molar ratio of the precipitant a to the complexing agent a is 5: 1.
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of the lithium ions to the total amount of nickel, cobalt, and manganese in the material was 108%.
In this example, the molar ratio of titanium dioxide and ammonium chloride was 1:1, and the molar ratio of the total amount of titanium dioxide and ammonium chloride to the total amount of nickel cobalt manganese in the entire material was 2%.
In this embodiment, the solvent for wet ball milling is absolute ethyl alcohol, the ball milling speed is 400r/min, and the ball milling time is 4 hours.
Comparative example 1
The comparative example provides a preparation method of a modified ternary lithium ion battery anode material, which comprises the following steps:
respectively weighing nickel sulfate, cobalt sulfate and manganese sulfate according to the molar ratio of Ni to Co to Mn of 14 to 3 to obtain first mixed salt, uniformly dispersing the first mixed salt in deoxygenated high-purity water according to the proportion of 2moL/L, and preparing to obtain a first mixed salt solution. Under the protection of high-purity nitrogen atmosphere, simultaneously feeding a precipitator A, a complexing agent A and a first mixed salt solution in a parallel flow manner, feeding the mixture into a reaction kettle for precipitation reaction, controlling the precipitation temperature to be 55 ℃ and the pH value to be 11.1, carrying out coprecipitation reaction for 6 hours, and carrying out primary aging for 8 hours to prepare a precursor Ni precursor of the ternary lithium ion battery anode material0.75Co0.15Mn0.15(OH)2。
Filtering and washing the precursor of the ternary lithium ion battery anode material, drying at 105 ℃, carrying out wet ball milling on the precursor and a lithium source together, and then carrying out two-stage calcination (5 h at 550 ℃ and 15h at 830 ℃) in an oxygen atmosphere to obtain a ternary anode active material Li (Ni)0.7Co0.15Mn0.15)O2(denoted as NCM 701515).
In this example, the precipitant a is sodium hydroxide, and the complexing agent a is ammonia water.
In this example, the molar ratio of Li/(Ni + Co + Mn) was 1.05.
In this embodiment, the ball milling speed of the wet ball milling is 300r/min, and the ball milling time is 3 hours.
The ternary positive active material obtained in the embodiment is used as an experimental battery to perform electrochemical performance test, and has a specific discharge capacity of 148mAh/g at a multiplying power of 0.1C, 45mAh/g at a multiplying power of 5C, and 30.4% of that at 0.1C. The cyclic voltammogram is shown in FIG. 2 (A).
It is to be understood that the above-described embodiments are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. The modified ternary lithium ion battery positive electrode material is characterized in that the modified ternary lithium ion battery positive electrode is of a core-shell structure, an inner core of the modified ternary lithium ion battery positive electrode is a first nickel-cobalt-manganese ternary material, an outer shell of the modified ternary lithium ion battery positive electrode is a second nickel-cobalt-manganese ternary material, and the mass ratio of the outer shell to the inner core is 1: 8-10;
wherein the molar ratio of Ni to Co to Mn in the first nickel-cobalt-manganese ternary material is 13-15: 2-4;
the molar ratio of Ni to Co to Mn in the second nickel-cobalt-manganese ternary material is 0.5-2: 1:1, and lithium ions are doped in the second nickel-cobalt-manganese ternary material.
2. The modified ternary lithium ion battery positive electrode material of claim 1, wherein the second nickel cobalt manganese ternary material is further doped with halogen and metal elements;
the halogen is any one of F, Cl and Br;
the metal element is one or more of Ti and Mg;
the molar ratio of the total amount of the halogen and the metal element to the total amount of the first nickel-cobalt-manganese ternary material and the second nickel-cobalt-manganese ternary material is 0.5-2%.
3. The modified ternary lithium ion battery positive electrode material of claim 2, wherein the halogen and metal elements are mixed in equimolar amounts.
4. The preparation method of the modified ternary lithium ion battery positive electrode material as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
s1, preparing a core material:
uniformly dispersing nickel salt, cobalt salt and manganese salt in a water solvent to prepare a first mixed salt solution, adding a precipitator A and a complexing agent A into the first mixed salt solution, then precipitating the first mixed salt solution for 5-7 hours at 50-60 ℃ and under the condition that the pH value is 10.5-11.5 in an inert atmosphere, and then performing primary aging for 7-9 hours to obtain an inner core material;
s2, preparing a precursor of the modified ternary lithium ion battery anode material:
uniformly dispersing nickel salt, cobalt salt and manganese salt in a water solvent to prepare a second mixed salt solution, simultaneously adding the second mixed salt solution, a precipitator B and a complexing agent B into the obtained core material in an inert atmosphere, precipitating for 2-6 h under the conditions of 50-60 ℃ and pH of 10-11, then performing secondary aging for 7-9 h, and coating a layer of core material on the surface of the core material to obtain a modified ternary lithium ion battery anode material precursor;
s3, uniformly mixing the precursor of the modified ternary lithium ion battery positive electrode material with the doping elements by wet ball milling, and then carrying out sectional calcination on the mixture in an oxygen atmosphere to obtain the modified ternary lithium ion battery positive electrode material;
the doping element is a lithium source, or a lithium source, halogen and a metal element.
5. The preparation method of claim 4, wherein the wet ball milling is performed in an organic solvent, the ball milling rotation speed is 200-400 r/min, and the ball milling time is 2-4 h.
6. The preparation method according to claim 4, wherein the step calcination is calcination at 500-600 ℃ for 4-6 h, calcination at 800-850 ℃ for 12-18 h, and calcination at 850-950 ℃ for 0.5-2 h.
7. The method according to claim 4, wherein the first mixed salt solution contains the total amount of the nickel salt, the cobalt salt and the manganese salt and the water solvent in a ratio of 1 to 3 mol/L;
the molar ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the precipitant A is 1: 1-3;
the molar ratio of the precipitant A to the complexing agent A is 3-5: 1.
8. The method according to claim 7, wherein the second mixed salt solution contains the total amount of the nickel salt, the cobalt salt and the manganese salt and the water solvent in a ratio of 1 to 3 mol/L;
the molar ratio of the total amount of the nickel salt, the cobalt salt and the manganese salt to the precipitant B is 1: 1-3;
the molar ratio of the precipitant B to the complexing agent B is 3-5: 1.
9. The preparation method according to claim 8, wherein the precipitant A and the precipitant B are both one or two of sodium hydroxide and potassium hydroxide;
and the complexing agent A and the complexing agent B are both ammonia water.
10. Use of the modified ternary lithium ion battery positive electrode material according to any one of claims 1 to 3 in a lithium ion battery.
CN202111045232.5A 2021-09-07 2021-09-07 Modified ternary lithium ion battery positive electrode material and preparation method and application thereof Pending CN113745484A (en)

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