CN112510194A - Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery - Google Patents

Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery Download PDF

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CN112510194A
CN112510194A CN201910872886.1A CN201910872886A CN112510194A CN 112510194 A CN112510194 A CN 112510194A CN 201910872886 A CN201910872886 A CN 201910872886A CN 112510194 A CN112510194 A CN 112510194A
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ternary
cathode material
ternary cathode
ion battery
lithium ion
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CN112510194B (en
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范宇琦
付强
陈靖华
曹文玉
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Huizhou BYD Industrial 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
    • H01M4/48—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
    • 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
    • H01M4/52—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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 disclosure relates to a ternary cathode material of a lithium ion battery, a preparation method thereof and the lithium ion battery, wherein the particle surface of the ternary cathode material is of a lamellar structure, and the lamellar structure is provided with a plurality of stacked lamellar units; the thickness of the lamella unit is 100-200nm, and the length of the lamella is about 300-600 nm; d of ternary cathode material101400-1800nm, ternary positive electrode material D902900-50Is 2000-2500nm, and the specific surface area of the ternary cathode material is 18000-35000cm2(ii) in terms of/g. Compared with the traditional secondary ball small particles, the lithium ion battery anode material disclosed by the invention is more tightly combined and has better mechanical strength, and the unique hierarchical lamellar structure of the lithium ion battery anode material has a richer surface than that of a single crystal material, so that the electrode/electrolyte interface is enlarged, and the lithium ion battery anode material is more excellent in mechanical strengthIs beneficial to the intercalation/deintercalation process of lithium ions, thereby having higher capacity exertion.

Description

Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery
Technical Field
The disclosure relates to the field of lithium ion batteries, in particular to a ternary cathode material of a lithium ion battery, a preparation method of the ternary cathode material and the lithium ion battery.
Background
With the high-speed expansion of the lithium ion battery market and the advantage of the ternary cathode material in terms of high specific capacity, the demand of the ternary cathode material is increasing day by day. At present, common particle shapes of the conventional ternary cathode material are large single crystal type and secondary spherical type. Different appearances have different performance characterization characteristics, and the most suitable ternary cathode material with a specific appearance can be selected according to different use scenes of the material. At present, the process method for producing the ternary cathode material is mainly a high-temperature solid phase method, and most manufacturers on the market produce the large single-crystal and secondary-sphere ternary cathode material which is mainly used for manufacturing power batteries.
However, the secondary spherical particles are easy to generate secondary spherical crushing in rolling and battery cycling processes, and the large single crystal particles have limitation on the insertion/extraction of lithium ions in the battery cycling process, so that the capacity of the ternary cathode material is not favorably exerted.
Disclosure of Invention
The purpose of the present disclosure is to overcome the problems of the existing ternary cathode material in terms of mechanical strength and electrochemical properties, and to provide a ternary cathode material with better mechanical strength and electrochemical properties.
In order to achieve the above object, a first aspect of the present disclosure provides a ternary cathode material for a lithium ion battery, wherein a particle surface of the ternary cathode material is a lamellar structure, and the lamellar structure has a plurality of lamellar units stacked; the thickness of the lamella unit is 100-200nm, and the length is 300-600 nm; d of the ternary cathode material101400-1800nm, D of the ternary cathode material902900-50Is 2000-2500nm, and the specific surface area of the ternary cathode material is 18000-35000cm2/g。
Optionally, the ternary cathode material contains a ternary active component containing a compound of formula LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2; based on the total weight of the ternary cathode materialThe content of the ternary active component is 98.5-99.9 wt% based on the weight.
Optionally, the ternary cathode material further contains a Bi element and a V element, and the molar ratio of the Bi element to the V element is (0.5-0.8): (0.2-0.5).
In order to achieve the above object, a second aspect of the present disclosure provides a method for preparing a ternary cathode material for a lithium ion battery according to the first aspect of the present disclosure, the method comprising: mixing a ternary positive electrode material precursor, a lithium source and an additive and calcining; the additive contains V2O5And Bi2O3。
Optionally, the lithiation ratio of the lithium ion battery ternary cathode material is 1.005-1.1; the dosage of the additive is 0.1-1.5 wt% based on the total weight of the ternary cathode material of the lithium ion battery.
Optionally, the molar ratio of Bi element to V element in the additive is (0.5-0.8): (0.2-0.5); the lithium source comprises one or more of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate and lithium acetate, and the particle size of the ternary positive electrode material precursor is 2000-6000 nm.
Alternatively, the conditions of the calcination treatment include: the calcination is carried out in a pure oxygen atmosphere, the calcination temperature is 650-950 ℃, and the calcination treatment time is 10-30 h.
Optionally, the method further comprises: carrying out spray granulation on the slurry, and drying for 6-72 hours at the temperature of 80-120 ℃ to obtain a precursor of the ternary cathode material of the lithium ion battery; the slurry contains Ni, Mn and Co.
Optionally, the method further comprises: mixing and reacting a solution containing Ni ions, a solution containing Mn ions and a solution containing Co ions with a complexing agent and a precipitator to obtain the slurry; the pH value of the slurry is 10.0-11.0, the mixing temperature is 45-65 ℃, and the reaction time is 12-72 hours; the molar ratio of the amount of the Ni ion-containing solution, the Mn ion-containing solution and the Co ion-containing solution is 1: (0.055-0.34): (0.055-0.34).
In order to achieve the above object, a third aspect of the present disclosure provides a lithium ion battery containing the lithium ion battery ternary cathode material of the first aspect of the present disclosure.
The ternary cathode material with the hierarchical lamellar structure is prepared by mixing the lithium ion battery ternary cathode material precursor, the lithium source and the additive and carrying out calcination treatment, has better mechanical strength due to tighter combination among the particles compared with the traditional secondary ball particles, has richer surface compared with a single crystal material due to the unique hierarchical lamellar structure, increases the electrode/electrolyte interface, is more beneficial to the insertion/extraction process of lithium ions, and has higher capacity.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
fig. 1 is an SEM image (magnification 30K times) of a lamellar structure ternary cathode material prepared in example 1 of the present disclosure;
fig. 2 is an SEM image (magnification 5K times) of a lamellar structure ternary cathode material prepared in example 1 of the present disclosure;
fig. 3 is an XRD pattern of the lamellar structure ternary positive electrode material prepared in example 1 of the present disclosure;
fig. 4 is an SEM image (magnification 30K times) of the sheet structure ternary cathode material prepared in example 1 of the present disclosure after rolling under a pressure of 6 MPa;
fig. 5 is an SEM image (magnification 5K times) of the sheet structure ternary cathode material prepared in example 1 of the present disclosure after rolling under a pressure of 6 MPa;
fig. 6 is a charge-discharge curve diagram of the lamellar structure ternary cathode material prepared in example 1 of the present disclosure;
fig. 7 is an SEM image (30K x magnification) of a commercial quadratic spherical morphology ternary positive electrode material in comparative example 1 of the present disclosure;
fig. 8 is an SEM image (5K x magnification) of a commercial quadratic spherical morphology ternary positive electrode material in comparative example 1 of the present disclosure;
fig. 9 is an SEM image (30K times magnification) of a commercial secondary sphere morphology ternary positive electrode material of comparative example 1 of the present disclosure after 6MPa pressure rolling;
fig. 10 is an SEM image (5K times magnification) of a commercial secondary sphere morphology ternary positive electrode material of comparative example 1 of the present disclosure after 6MPa pressure rolling;
fig. 11 is an SEM image (magnification 10K times) of a single crystal morphology ternary cathode material prepared in comparative example 2 of the present disclosure;
fig. 12 is an SEM image (5K x magnification) of a single crystal morphology ternary cathode material prepared in comparative example 2 of the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure provides a ternary cathode material for a lithium ion battery, wherein the particle surface of the ternary cathode material is of a lamellar structure, and the lamellar structure is provided with a plurality of stacked lamellar units; the thickness of the lamella unit can be 100-200nm, and the length can be 300-600 nm; d of ternary cathode material10Can be 1400-1800nm, D of ternary cathode material90Can be 2900-50Can be 2000-2500nm, and the specific surface area of the ternary cathode material can be 18000-35000cm2/g。
The ternary cathode material with the hierarchical lamellar structure is prepared by mixing the lithium ion battery ternary cathode material precursor, the lithium source and the additive and carrying out calcination treatment, has better mechanical strength due to tighter combination among the particles compared with the traditional secondary ball particles, has richer surface compared with a single crystal material due to the unique hierarchical lamellar structure, increases the electrode/electrolyte interface, is more beneficial to the insertion/extraction process of lithium ions, and has higher capacity.
According to the disclosure, the thickness of the sheet layer unit can be 120-170nm, the length can be 400-550nm, and the D of the ternary cathode material10Can be 1500-1700nm, D of ternary anode material90Can be 3000-3200nm, D of ternary cathode material50Can be 2150-2(ii) in terms of/g. Wherein, the thickness and length values of the ternary cathode material are the average value of the test results of the scanning electron microscope, D10It is meant a particle size having a cumulative particle distribution of 10%, i.e., the volume content of particles smaller than this particle size is 10% of the total particles. D90It is meant a particle size having a cumulative particle distribution of 90%, i.e., the volume fraction of particles smaller than this particle size is 90% of the total particles. D50The particle size corresponding to the cumulative percentage of the particle size distribution of the sample reaching 50% means that the particles having a particle size greater than 50% are present and the particles having a particle size less than 50% are present. Within the above range, the ternary cathode material of the present disclosure may be made to have better mechanical strength and electrochemical properties.
According to the present disclosure, a ternary positive electrode material contains a ternary active component. In one embodiment of the present disclosure, the composition of the ternary active component is not particularly limited, and preferably, the ternary active component contains Li, Ni, Mn, and Co elements. In one embodiment, the ternary active component may comprise a compound of the formula LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2; preferably, 0.65 ≦ x ≦ 0.85, 0.075 ≦ y ≦ 0.175. In another embodiment of the present disclosure, the amount of the ternary active component may vary over a wide range. Preferably, the ternary active component may be contained in an amount of 98.8 to 99.85 wt%, more preferably 99.2 to 99.8 wt%, based on the total weight of the ternary positive electrode material. Within the preferable content range, the proportion of the ternary active component and the additive is proper, the ternary active component has a hierarchical lamellar structure with a better structure, and the crushing resistance, the rate capability and the first charge-discharge efficiency of the ternary cathode material can be further improved.
In one embodiment according to the present disclosure, the ternary cathode material may further contain a Bi element and a V element, and the total weight of the Bi element and the V element may vary within a wide range, for example, the total weight of the Bi element and the V element may be 0.05 to 1.0 wt%, for example, 0.8 wt%, preferably 0.1 to 0.6 wt%, for example, 0.5 wt%, based on the total weight of the ternary cathode material; further, the relative content of the Bi element to the V element in the ternary positive electrode material may vary over a wide range, and the molar ratio of the Bi element to the V element is preferably (0.5 to 0.8): (0.2-0.5), more preferably (0.55-0.7): (0.3-0.45). In the preferred embodiment, the ternary cathode material can form a more tightly combined hierarchical lamellar structure, and the specific surface area and the mechanical property are further improved.
A second aspect of the present disclosure provides a method of preparing a lithium ion battery ternary cathode material of the first aspect of the present disclosure, which may include: mixing a precursor of a ternary positive electrode material of the lithium ion battery, a lithium source and an additive, and calcining; the additive may contain V2O5And Bi2O3。
In one embodiment of the present disclosure, Bi is used2O3And V2O5The additive is introduced to enable the ternary material to maintain the lamellar stacking morphology characteristic of a precursor in the sintering process, the transmission and diffusion of Li are not hindered, and the ternary cathode material with good crystallization, excellent electrochemical performance and better particle bonding strength can be obtained.
In accordance with the present disclosure, the additive may also contain WO3、CeO2、MoO3And Ta2O5One or more of them.
In the method according to the present disclosure, the mixing may be performed by a method conventionally used by those skilled in the art, for example, a mechanical mixing method may be used, and the stirring rate may be selected according to the requirement, for example, may be 500-.
In a specific embodiment of the present disclosure, the lithiation ratio of the prepared lithium ion battery ternary cathode material is 1.005-1.1, preferably 1.01-1.06, so as to further improve the mechanical properties and electrochemical properties of the ternary cathode material. Wherein, the lithiation ratio is the ratio of the mole number of lithium element contained in the prepared ternary cathode material to the total mole number of three elements of nickel, cobalt and manganese.
According to the present disclosure, the amount of the additive may vary within a wide range, and in one embodiment of the present disclosure, the amount of the additive may be 0.1 to 1.5 wt%, preferably 0.2 to 0.8 wt%, based on the total weight of the prepared ternary cathode material, so as to better maintain the lamellar stacking morphology of the ternary material precursor and enhance the mechanical properties.
According to the present disclosure, the molar ratio of the Bi element to the V element in the additive may vary within a wide range, preferably (0.5-0.8): (0.2-0.5), more preferably (0.55-0.7): (0.3-0.45) to further maintain a good stacking morphology of the ternary cathode material sheets.
According to the present disclosure, the type of the lithium source is not particularly required, and is preferably one or more of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate and lithium acetate, and is more preferably lithium hydroxide monohydrate and lithium carbonate; the particle size of the precursor can vary within a wide range, and preferably, the particle size of the precursor can be 2000-6000nm, and more preferably 2400-5000 nm.
The calcination treatment may be according to the present disclosure a treatment method and conditions conventional in the art. In one embodiment, the conditions of the calcination treatment may include: the calcination can be carried out in a pure oxygen atmosphere, the calcination temperature can be 650-950 ℃, and the calcination treatment time can be 10-30 h. Preferably, the calcination can be carried out in a pure oxygen atmosphere, the calcination temperature can be 700-900 ℃, and the calcination treatment time can be 12-24 h.
The precursor of the ternary cathode material may be conventionally used by those skilled in the art, for example, the precursor of the nickel-cobalt-manganese ternary cathode material, and the method for preparing the precursor is not particularly limited and may be conventionally used by those skilled in the art. In a preferred embodiment, the method may further comprise: spray granulating the slurry, and drying for 12-48 hours at 80-120 ℃ to obtain a precursor of the ternary cathode material of the lithium ion battery; the slurry may contain Ni element, Mn element, and Co element. The spray granulation can be performed in the equipment conventionally used by those skilled in the art, for example, a spray granulator and an ultrasonic atomizer can be used, preferably, the spray granulation process is performed by using an ultrasonic atomizer, the oscillation frequency of the ultrasonic atomizer can be 5000-10000MHz, nitrogen or inert gas is used as carrier gas, and the atomized particles are passed into a dryer or drying oven for drying treatment, the drying temperature is not particularly limited, and can be selected according to actual needs.
According to the present disclosure, a solution containing Ni ions, a solution containing Mn ions, and a solution containing Co ions may be mixed with a complexing agent and a precipitating agent and reacted to obtain the above-mentioned slurry containing Ni, Mn, and Co elements; the pH value of the slurry can be 10.0-11.0, the mixing temperature can be 45-65 ℃, and the reaction time can be 12-72 hours; the molar ratio of the amounts of the Ni ion-containing solution, the Mn ion-containing solution, and the Co ion-containing solution, in terms of Ni, Mn, and Co, may be 1: (0.055-0.34): (0.055-0.34); preferably, the pH of the slurry may be 10.3 to 10.7, the mixing temperature may be 50 to 60 ℃ and the reaction time may be 18 to 54 hours. The molar ratio of the amounts of the Ni ion-containing solution, the Mn ion-containing solution, and the Co ion-containing solution, in terms of Ni, Mn, and Co, may be 1: (0.055-0.34): (0.055-0.34), preferably 1: (0.12-0.3): (0.12-0.3). Within the preferable condition range, the reaction components can further and fully react, and the ternary cathode material with a specific graded lamellar morphology is formed, so that the electrochemical performance of the prepared ternary cathode material for the lithium ion battery is further improved.
In a third aspect of the present disclosure, a lithium ion battery is provided, which contains the lithium ion battery ternary cathode material provided in the first aspect of the present disclosure. The lithium ion battery disclosed by the invention has excellent electrochemical performance, higher first-turn discharge voltage and coulombic efficiency, and the electrode material has more efficient capacity exertion.
The lithium ion battery disclosed by the disclosure further comprises a positive electrode, a negative electrode, a diaphragm and an electrolyte, wherein the positive electrode contains the ternary positive electrode material disclosed by the disclosure, and the negative electrode, the diaphragm and the electrolyte are well known to those skilled in the art and are not described herein in detail, and the lithium ion battery can be prepared by a method conventionally adopted by those skilled in the art. The specific form of the lithium ion battery is not limited, and the lithium ion battery can be a soft package battery or a button battery.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby. In the following examples and comparative examples of the present disclosure, raw materials used were commercially available reagents without being described to the contrary.
Example 1
a. Selecting nNickel (II)：nCobalt：nManganese oxide0.8: 0.1: 0.1 proportion, nickel sulfate, cobalt sulfate and manganese sulfate are used as raw materials to prepare a mixed solution with the total metal ion concentration of 2 mol/L; preparing 2mol/L NaOH solution as a precipitator; 2mol/L ammonia water is prepared as a complexing agent.
b. Adding a sodium hydroxide solution and an ammonia water solution into a mother solution which is a mixed metal ion solution at a certain speed, controlling the pH value of a reaction system to be 10.5 by adjusting a valve and a flowmeter, controlling the reaction temperature to be 55 ℃, controlling the reaction time to be 18h, and controlling the stirring speed to be 300r/min, carrying out solid-liquid separation on the feed solution after the reaction is finished, and drying the collected solid product at 80 ℃ for 24h to obtain a precursor with the particle size of 3800 nm.
c. Taking lithium hydroxide as a lithium source, blending according to the lithiation ratio of 1.02 and a dried precursor, and adding 0.5 weight percent of Bi based on the total weight of the ternary cathode material2O3And V2O5(the molar ratio of the Bi element to the V element is 0.7: 0.3), and the mixture is poured into a mortar to be calcined. The temperature rising speed in the calcining process is 5 ℃/min, the temperature is raised to 750 ℃, then the temperature is preserved for 15h, the sintering atmosphere is oxygen, and the sintering furnace is naturally cooled to the room temperature after the temperature preservation.
d. And coarsely crushing the cooled material, then performing air crushing by using an air crusher device, wherein the air crushing pressure is 0.15MPa, and drying the air-crushed material at 120 ℃ for 24 hours.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive used does not affect the sintering process of the ternary cathode material, the product is the nickel cobalt lithium manganate ternary cathode material, and the scanning electron microscope result (as shown in figure 1 and figure 2) shows that the sample has a hierarchical lamellar structure and is assembled by lamellar layers with the thickness of 150nm and the length of 430nm, and Bi2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1700nm, D903100nm, D502300nm and a specific surface area test result of 20500cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 216.7mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 91.3%. The ternary cathode material with the hierarchical lamellar structure has no obvious particle fracture after being rolled under the pressure of 6MPa (as shown in figures 4 and 5). The ternary positive electrode material was ground and then subjected to XRD measurement, and the results are shown in fig. 3.
Example 2
The ternary cathode material prepared by the method of example 1 is different in that in the step b, the pH of the reaction system is controlled to be 10.2, the reaction temperature is 50 ℃, the reaction time is 14h, the stirring speed is 350r/min, the collected solid product is dried at 100 ℃ for 15h, and the particle size of the obtained precursor is 1600 nm.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of the nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is assembled by lamellar layers with the thickness of 120nm and the length of 330nm, and Bi is added2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1400nm, D90Is 2900nm, D502000nm, and 26700 as a result of the specific surface area testcm2And the lithium iron phosphate/g is used as a ternary positive material to be assembled into a button cell, the initial discharge reaches 215mAh/g under the multiplying power of 0.1C, and the coulombic efficiency of the first circle reaches 86.9 percent.
Example 3
The ternary cathode material prepared by the method of example 1 is different in that in the step b, the pH of the reaction system is controlled to be 10.7, the reaction temperature is 55 ℃, the reaction time is 24 hours, the stirring speed is 280r/min, the collected solid product is dried at 90 ℃ for 30 hours, and the particle size of the obtained precursor is 6200 nm.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is assembled by lamellar layers with the thickness of 180nm and the length of 540nm, and Bi is formed2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1800nm, D903250nm, D502500nm, and the specific surface area test result is 18600cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 208.8mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency reaches 89.1 percent.
Example 4
A ternary positive electrode material was prepared by the method of example 1, except that 0.5 wt% of Bi was added based on the total weight of the ternary positive electrode material in step c2O3And V2O5(the molar ratio of the Bi element to the V element is 0.3: 0.7).
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the nickel cobalt lithium manganate ternary cathode material, and the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is formed by sheets with the thickness of 150nm and the length of 430nmIs assembled in layers of Bi2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1700nm, D90Is 3200nm, D50Is 2350nm, and the specific surface area test result is 20200cm2And the lithium iron phosphate/g is used as a ternary positive material to be assembled into a button cell, the first discharge reaches 209.4mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 89.8 percent.
Example 5
A ternary positive electrode material was prepared by the method of example 1, except that 0.5 wt% of Bi was added based on the total weight of the ternary positive electrode material in step c2O3And V2O5(the molar ratio of the Bi element to the V element is 0.9: 0.1).
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of the nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is assembled by lamellar layers with the thickness of 150nm and the length of 410nm, and Bi is added2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10At 1600nm, D903100nm, D502300nm and a specific surface area test result of 20900cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 210.5mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 90.2%.
Example 6
The ternary cathode material was prepared by the method of example 1, except that the calcination process in step c was carried out for 42 hours after heating to 550 ℃.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive has no influence on the ternary cathode materialThe product is the nickel cobalt lithium manganate ternary positive electrode material, and the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is formed by assembling lamellae with the thickness of 130nm and the length of 340nm, and Bi2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1400nm, D90Is 3000nm, D50Is 2100nm, and the specific surface area test result is 23100cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 211.2mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 90.1%.
Example 7
The ternary cathode material was prepared by the method of example 1, except that in step c the calcination process was ramped up to 1050 ℃ and held for 6 h.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of the nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is assembled by lamellae with the thickness of 170nm and the length of 560nm, and Bi is formed by the assembly of the lamellae2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10At 1750nm, D903300nm, D502500nm, the specific surface area test result is 19200cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 203.7mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 86.4%.
Example 8
A ternary cathode material was prepared using the method of example 1, except that lithium nitrate was used as the lithium source in step c.
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive used does not affect the ternary positive electrode materialThe product is the nickel cobalt lithium manganate ternary positive electrode material in the sintering process of the material, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is formed by assembling lamellae with the thickness of 150nm and the length of 420nm, and Bi2O3And V2O5The introduction of the precursor enables the ternary material to maintain the sheet stacking morphology characteristic of the precursor in the sintering process, and the Malvern particle size analysis result shows that D10Is 1700nm, D903100nm, D502300nm, and 20700cm of specific surface area test result2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 214.8mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency reaches 89.5 percent.
Comparative example 1
The phase of choice being Li (Ni)0.8Co0.1Mn0.1)O2The commercialized ternary cathode material with the secondary sphere morphology is used as a cathode for experiments, the scanning electron microscope results (shown in fig. 7 and 8) show that a sample is a secondary sphere composed of primary particles, the primary particles are blocky small particles with the particle size of about 200-600 nm, and the Malvern particle size analysis result shows that D is the particle size10Is 6000nm, D90Is 9700nm, D50The particle size is 16500nm, and the specific surface area test result is 4200cm2The first discharge reaches 214mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 90.1 percent. The ternary cathode material with the secondary sphere morphology has obvious particle breakage after being rolled under the pressure of 6MPa (as shown in figures 9 and 10).
Comparative example 2
a. Selecting nNickel (II)：nCobalt：nManganese oxide0.8: 0.1: 0.1 proportion, preparing a mixed solution with the total metal ion concentration of 2.5mol/L by using nickel chloride, cobalt chloride and manganese chloride as raw materials; preparing 2.5mol/L NaOH solution as a precipitator; 2.5mol/L ammonia water is prepared as a complexing agent.
b. Adding a sodium hydroxide solution and an ammonia water solution into a mother solution which is a mixed metal ion solution at a certain speed, controlling the pH value of a reaction system to be 11.0 by adjusting a valve and a flowmeter, controlling the reaction temperature to be 50 ℃, the reaction time to be 20h, and the stirring speed to be 500r/min, carrying out solid-liquid separation on a feed liquid after the reaction is finished, and drying the collected solid product at 120 ℃ for 24h to obtain a precursor with the particle size of 3900 nm.
c. And taking lithium hydroxide as a lithium source, mixing the lithium source with the dried precursor according to the lithiation ratio of 1.04, and loading the mixed material into a pot for calcining. The heating rate is 3 ℃/min, the temperature is raised to 850 ℃, the temperature is kept for 10h, the sintering atmosphere is oxygen, and the temperature is naturally cooled to the room temperature after the temperature is kept.
d. And coarsely crushing the cooled material, then performing gas crushing by using a gas crusher device, wherein the gas crushing pressure is selected to be 0.3MPa, and drying the material subjected to gas crushing at 80 ℃ for 24 hours.
Phase analysis results the phase of the sample obtained by preparation was Li (Ni)0.8Co0.1Mn0.1)O2The scanning electron microscope results (as shown in FIGS. 11 and 12) show that the sample is large single crystal particles, and the Malvern particle size analysis result shows that D10Is 2200nm, D90Is 8200nm, D503800nm, 11100cm in specific surface area2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 199mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 84.7%.
Comparative example 3
A ternary positive electrode material was prepared by the method of example 1, except that in step c, an equivalent amount of V was used2O5Replacement of Bi2O3。
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of the nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is formed by assembling lamellar layers with the thickness of 150nm and the length of 430nm, and the Malvern particle size analysis result shows that D is the particle size of the lithium manganate10At 1600nm, D90Is 3200nm, D50Is 2350nm, and the specific surface area test result is 20300cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 200.5mAh/g under the multiplying power of 0.1C, and the first coulomb efficiency reaches 86.7 percent.
Comparative example 4
A ternary positive electrode material was prepared by the method of example 1, except that in step c, an equivalent amount of Bi was used2O3Alternative V2O5。
The test result shows that the phase of the sample prepared by the method is Li (Ni)0.8Co0.1Mn0.1)O2The additive does not influence the sintering process of the ternary cathode material, the product is the ternary cathode material of the nickel cobalt lithium manganate, the scanning electron microscope result shows that the sample has a hierarchical lamellar structure and is formed by assembling lamellae with the thickness of 150nm and the length of 420nm, and the Malvern particle size analysis result shows that D is the particle size of the lithium manganate10Is 1700nm, D90Is 3150nm, D50Is 2200nm and the specific surface area test result is 20800cm2And the lithium iron phosphate/g is used as a ternary positive electrode material to be assembled into a button cell, the first discharge reaches 199.8mAh/g under the multiplying power of 0.1C, and the first coulombic efficiency reaches 87.1 percent.
Test example
(1) X-ray diffraction (XRD) testing
Determining the phase composition of the sample by using D8 advanced X-ray diffractometer manufactured by Bruker company, and selecting Cu Ka radiation and wavelength
Figure BDA0002203401090000151
The voltage was 40kV, the current was 40mA, the test range 2 θ was 10 ° to 80 °, and the test sample was a ground powder sample.
(2) Scanning Electron Microscope (SEM) testing
The microstructure of the ternary positive electrode material powder was measured by a scanning electron microscope of JSM-7800, manufactured by Japan K.K., at a scanning voltage of 5KV and a magnification of 5 Kx, 10 Kx, or 30 Kx. And adhering the powder sample on a conductive adhesive tape, spraying gold, and drying and storing the sample in a vacuum drying oven before testing.
The rolling test of the ternary cathode material under the pressure of 6MPa is carried out on a hydraulic electric double-roller machine, and the SEM test is carried out after the rolling.
(3) Specific surface area test
The specific surface area of the ternary positive electrode material was measured using a BET multipoint method using a specific surface area and pore analyzer model No. 3H-3000PS2 manufactured by Bechard instruments & science and technology Ltd.
(4) Malvern particle size test
Particle size distribution testing of the material was performed using a Mastersizer 3000.
(5) Battery preparation and electrochemical Performance testing
According to the mass ratio of 100: 3: 3 adding a certain amount of N-methyl pyrrolidone (NMP) into the active material, the conductive agent (0.5CNT +0.5GN) and the polyvinylidene fluoride (PVDF), uniformly mixing, drying in vacuum at 110 ℃, pressing into a wafer as a positive electrode, taking a metal lithium sheet as a negative electrode, taking a Celgard 2300 microporous membrane as a diaphragm, and taking 1mol/L LiPF electrolyte6Ethylene Carbonate (EC) + dimethyl carbonate (DMC) (volume ratio 1: 1) assembled into CR2025 button cells in a glove box. The electrochemical performance test is carried out by using a Xinwei 3008 battery test system under the test condition of room temperature of 25 ℃. The charge-discharge cut-off voltage is 2.5-4.3V (vs. Li/Li +), and the test multiplying power is 0.1C. The test results are shown in tables 1 and 2.
TABLE 1
Figure BDA0002203401090000161
TABLE 2
Figure BDA0002203401090000162
Figure BDA0002203401090000171
As can be seen from the above examples 1 to 8, the ternary cathode material having a lamellar structure prepared by the method of the present disclosure has more excellent electrochemical properties than the conventional ternary cathode material of comparative examples 1 to 2 and the ternary cathode material of comparative examples 3 to 4 in which only one oxide additive is added; also, it can be seen from fig. 4, 5, 9, and 10 that the sheet structure ternary cathode material of the present disclosure has higher mechanical strength than the secondary sphere morphology ternary cathode material.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (10)

1. The ternary cathode material of the lithium ion battery is characterized in that the particle surface of the ternary cathode material is of a lamellar structure, and the lamellar structure is provided with a plurality of stacked lamellar units; the thickness of the lamella unit is 100-200nm, and the length is 300-600 nm; d of the ternary cathode material101400-1800nm, D of the ternary cathode material902900-50Is 2000-2500nm, and the specific surface area of the ternary cathode material is 18000-35000cm2/g。
2. The ternary positive electrode material according to claim 1, comprising a ternary active component comprising a compound of formula LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, and y is more than or equal to 0.05 and less than or equal to 0.2; the content of the ternary active component is 98.5-99.9 wt% based on the total weight of the ternary cathode material.
3. The ternary positive electrode material according to claim 2, further comprising a Bi element and a V element; the molar ratio of the Bi element to the V element is (0.5-0.8): (0.2-0.5).
4. A method for preparing a ternary cathode material of a lithium ion battery, which is characterized by comprising the following steps: mixing a ternary positive electrode material precursor, a lithium source and an additive and calcining; the additive contains V2O5And Bi2O3。
5. The method of claim 4, wherein the lithium ion battery ternary positive electrode material has a lithiation ratio of 1.005 to 1.1; the dosage of the additive is 0.1-1.5 wt% based on the total weight of the ternary cathode material of the lithium ion battery.
6. The method according to claim 4, wherein the molar ratio of the Bi element to the V element in the additive is (0.5-0.8): (0.2-0.5); the lithium source comprises one or more of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate and lithium acetate, and the particle size of the ternary positive electrode material precursor is 2000-6000 nm.
7. The method according to any one of claims 4 to 6, wherein the conditions of the calcination treatment include: the calcination is carried out in a pure oxygen atmosphere, the calcination temperature is 650-950 ℃, and the calcination treatment time is 10-30 h.
8. The method according to any one of claims 4-6, further comprising: carrying out spray granulation on the slurry, and drying for 6-72 hours at the temperature of 80-120 ℃ to obtain a precursor of the ternary cathode material of the lithium ion battery; the slurry contains Ni, Mn and Co.
9. The method of claim 8, further comprising: mixing and reacting a solution containing Ni ions, a solution containing Mn ions and a solution containing Co ions with a complexing agent and a precipitator to obtain the slurry; the pH value of the slurry is 10.0-11.0, the mixing temperature is 45-65 ℃, and the reaction time is 12-72 hours; the molar ratio of the amount of the Ni ion-containing solution, the Mn ion-containing solution and the Co ion-containing solution is 1: (0.055-0.34): (0.055-0.34).
10. A lithium ion battery comprising the lithium ion battery ternary positive electrode material according to any one of claims 1 to 3.
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