CN117012961A - Quaternary doped lithium cobaltate modified material and preparation method and application thereof - Google Patents

Quaternary doped lithium cobaltate modified material and preparation method and application thereof Download PDF

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CN117012961A
CN117012961A CN202310653817.8A CN202310653817A CN117012961A CN 117012961 A CN117012961 A CN 117012961A CN 202310653817 A CN202310653817 A CN 202310653817A CN 117012961 A CN117012961 A CN 117012961A
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ball milling
quaternary
temperature
modified material
hours
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许鑫
师伟宸
成永红
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Xian Jiaotong University
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Xian Jiaotong University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0422—Cells or battery with cylindrical casing
    • H01M10/0427—Button cells
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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

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Abstract

The invention provides a quaternary doped lithium cobaltate modified material, a preparation method and application thereof, firstly, li is mixed with 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder is ball milled according to a certain stoichiometric ratio to obtain a uniformly mixed solution, and thenAnd drying the obtained solution, grinding the dried product, calcining at high temperature for two times at different temperatures to obtain a modified lithium cobalt oxide positive electrode material, uniformly mixing the positive electrode material with a conductive agent and a binder, and assembling the mixture with a diaphragm, a negative electrode and an electrolyte to form the high-performance lithium ion battery. The invention is characterized in that based on the simple synthesis means of the high-temperature solid phase method, the modified lithium cobalt oxide anode material which has simple steps, less time consumption and better cycle stability and discharge specific capacity under high charge cut-off voltage is prepared.

Description

Quaternary doped lithium cobaltate modified material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical power supplies, and particularly relates to a quaternary doped lithium cobalt oxide modified material, and a preparation method and application thereof.
Background
Lithium ion batteries play a vital role in daily life, especially in mobile phones, tablet computers, electric vehicles and stationary energy storage devices. Meanwhile, the emerging 5g age puts higher demands on the energy density and cycle life of lithium ion batteries. LiCoO 2 Has 274 mAh.g -1 While in practical application, only 50% of lithium ions can be reversibly and stably released. To obtain higher specific discharge capacity and energy density, liCoO is increased 2 The charge cut-off voltage of the positive electrode is an effective industrialized strategy. LiCoO, however 2 The rise of the charge cut-off voltage causes a series of adverse reactions such as electrode interface degradation, lattice oxygen release and the like, so that the capacity of the battery is attenuated, and the practical application of the battery is greatly limited. Therefore, how to prepare a lithium cobaltate modified material with a certain structural stability at a charge cut-off voltage of 4.5V becomes a key to solve the above-mentioned problems.
Disclosure of Invention
The invention aims to provide a quaternary doped lithium cobalt oxide modified material, a preparation method and application thereof, so as to overcome the defect of structural distortion of a lithium cobalt oxide positive electrode material in the charge and discharge process of a lithium ion battery under high cut-off voltage.
The invention is realized by the following technical scheme:
a preparation method of a quaternary doped lithium cobaltate modified material comprises the following steps:
the first step: weighing raw materials Li according to stoichiometric ratio 2 CO 3 、Co 3 O 4 、BaCO 3 、TiO 2 MgO and Ga 2 O 3 Mixing to obtain mixed powder, n (Li) n (Co) n (Ba) n (Mg) n (Ga) =1.05 (0.6-0.98) (0.005-0.1) (0.01-0.1) (0.005-0.1);
and a second step of: taking absolute ethyl alcohol as a solvent, and placing the mixed powder into ball milling equipment for ball milling treatment to obtain a ball milling solution;
and a third step of: mixing the ball milling solution with a washing solution for washing ball milling equipment, volatilizing all absolute ethyl alcohol through heating to obtain a dry powder mixture, and grinding the dry powder mixture to obtain ground powder;
fourth step: presintering the ground powder to obtain a presintering product;
fifth step: and grinding the pre-sintered product, sintering again, and repeatedly grinding and sieving the sintered product to obtain the quaternary doped lithium cobalt oxide modified material.
Further, the second step specifically comprises: placing mixed powder into corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the ball milling tank for ball milling, pouring absolute ethyl alcohol with volume less than 1/3 of the volume of the ball milling tank and less than all mixed powder into the ball milling tank as solvent, capping the ball milling tank, placing the ball milling tank into a planetary ball mill, and stirring at 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
Further, the temperature at which the absolute ethanol was volatilized in the third step was 80 ℃.
Further, the conditions for the pre-sintering are set as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Further, the conditions for the re-sintering are set as follows: initial temperature of 30℃and 5℃min -1 Is heated to 800 ℃ of sintering temperature, kept at 800 ℃ for 10 hours of sintering, and then cooled to room temperature.
A quaternary doped lithium cobaltate modified material is prepared by adopting the preparation method.
The application of the quaternary doped lithium cobaltate modified material in the CR2032 button battery comprises the following steps:
1) Mixing the quaternary doped lithium cobaltate modified material with a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly stirring for 24 hours at 500r/min, coating the mixture on an aluminum foil, and drying the mixture at 80 ℃ for 12 hours to obtain a lithium ion battery positive plate of the modified material;
2) And (3) transferring the positive electrode plate of the lithium ion battery into a glove box, and assembling the CR2032 button battery in Ar inert gas atmosphere.
Further, the conductive agent is Super P, and the adhesive is polyvinylidene fluoride.
Further, in the assembling process of the step 2), a metal lithium wafer is adopted as a negative electrode, a diaphragm is Celgard2300, and an electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution of LiPF 6 The solvent of the organic solution is EC/EMC/DEC, and the volume ratio is 1:1:1.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention further strengthens Co-O bond by the cooperative doping of a plurality of metal elements, thereby inhibiting the escape of lattice oxygen and the Co of spinel phase on the surface in the charging and discharging process 3 O 4 Thereby enhancing the structural stability of lithium cobaltate, relieving the surface side reaction, expanding the interlayer spacing inside the lithium cobaltate lattice by the cooperative doping of a plurality of metal elements and promoting Li in the charge-discharge process + The specific discharge capacity of the lithium cobalt oxide anode material is improved.
The doping elements selected in the doping scheme of the invention have ionic radii Are all greater than->The doping elements replace Co sites in the lithium cobalt oxide structure, which tends to enlarge the interlayer spacing inside the lithium cobalt oxide crystal lattice, thereby promoting Li in the charge-discharge process + Thereby improving the discharge specific capacity of the lithium cobaltate cathode material. Meanwhile, electronegativity Ba (0.89), ti (1.5), mg (1.31) and Ga (1.81) of the doping elements are smaller than Co (1.88), so that the introduction of the doping elements can effectively relieve coulomb repulsion between Co and O, thereby increasing polarization energy of Co-O and improving stability of Co-O bonds. Inhibit lattice oxygen from escaping and surface spinel phase Co during charge and discharge 3 O 4 Thereby enhancing the structural stability of lithium cobaltate and relieving surface side reactions.
Drawings
FIG. 1 is LiCo prepared in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 SEM images of quaternary doped lithium cobaltate modified materials;
FIG. 2 is LiCo prepared in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 HRTEM diagram of quaternary doped lithium cobalt oxide modified material;
FIG. 3 is LiCo prepared in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 Quaternary doped lithium cobaltate modified material and LiCoO prepared in example 1 2 XRD pattern of lithium cobaltate;
FIG. 4 is a CV plot of an assembled lithium ion battery of example 9;
fig. 5 is a graph of cycle performance of lithium ion batteries assembled in examples 1, 3, 5, 7, 9;
fig. 6 is a graph showing the rate performance of the lithium ion batteries assembled in examples 1 and 9.
Detailed Description
The invention is described in further detail below, which is illustrative of the invention and not limiting.
The preparation method of the high-pressure lithium cobaltate material and multi-element co-doped high-pressure lithium cobaltate modified material comprises the following steps:
the first step: and weighing compound powder corresponding to each element in the target product according to the stoichiometric ratio determined by experimental design. LiCoO 2 Corresponding to Li of the element Li 2 CO 3 Co element corresponds to Co 3 O 4 The Ba element in the doping element corresponds to BaCO 3 Ti element corresponds to TiO 2 The Mg element corresponds to MgO, the Ga element corresponds to Ga 2 O 3 。
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 Is heated to 800 ℃ of sintering temperature, kept at 800 ℃ for 10 hours of sintering, and then cooled to room temperatureAnd repeatedly grinding and repeatedly sieving to obtain the final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the adhesive adopts polyvinylidene fluoride.
Seventh step: and (3) transferring the positive electrode plate obtained in the sixth step into a glove box (in Ar inert gas atmosphere), and assembling the CR2032 button battery. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 The organic solution (the solvent is EC/EMC/DEC, the volume ratio is 1:1:1) is assembled and then is kept stand for 24 hours for electrochemical testing.
Embodiments of the present invention will be described in detail below with reference to examples. This embodiment is a preferable embodiment of the present invention, and the scope of the present invention is not limited thereto. In the following examples, the methods and experimental equipment used were conventional methods and apparatus unless otherwise specified.
Example 1 (used as a comparative example)
The first step: selecting LiCoO 2 The sintering raw materials of the positive electrode material are respectively Li 2 CO 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co) =1.05: 1 weighing the related raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 2
The first step: liCo selection 0.975 Ba 0.01 Mg 0.01 Ga 0.005 O 2 Sintering raw material of quaternary doped lithium cobaltate modified materialThe materials are respectively Li 2 CO 3 、BaCO 3 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Mg): n (Ga) =1.05: 0.975:0.01:0.01:0.005 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 3
The first step: liCo selection 0.98 Ba 0.005 Mg 0.01 Ga 0.005 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Mg): n (Ga) =1.05: 0.98:0.005:0.1:0.005 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 4
The first step: liCo selection 0.75 Ba 0.1 Mg 0.1 Ga 0.05 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Mg): n (Ga) =1.05: 0.75:0.1:0.1:0.05 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 5
The first step: liCo selection 0.8 Ba 0.05 Mg 0.1 Ga 0.05 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Mg): n (Ga) =1.05: 0.8:0.05:0.1:0.05 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture ground in the third step into corundumThe porcelain boat is started in a muffle furnace for presintering, and specific sintering conditions are set as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 6
The first step: liCo selection 0.965 Ba 0.01 Ti 0.01 Mg 0.01 Ga 0.005 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Ti): n (Mg): n (Ga) =1.05: 0.6:0.1:0.1:0.1:0.1 weighing the relevant raw material powder, 5% excess Li 2 CO 3 For compensating for burn-inLi lost during the junction process.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 7
The first step: liCo selection 0.97 Ba 0.005 Ti 0.01 Mg 0.01 Ga 0.005 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Ti): n (Mg): n (Ga) =1.05: 0.97:0.005:0.01:0.01:0.005 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃at 5 ℃·min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 8
The first step: liCo selection 0.65 Ba 0.1 Ti 0.1 Mg 0.1 Ga 0.005 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Ti): n (Mg): n (Ga) =1.05: 0.65:0.1:0.1:0.1:0.0 5 weighing the related raw material powder, and 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: mixing the powder obtained in the first stepPlacing the mixture in a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume of less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank, placing the ball milling tank into a planetary ball mill for ball milling at 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (Ar inert gas atmosphere)In a gas atmosphere), a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
Example 9
The first step: liCo selection 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 Sintering raw materials of the quaternary doped lithium cobalt oxide modified material are respectively Li 2 CO 3 、BaCO 3 、TiO 2 、MgO、Ga 2 O 3 And Co 3 O 4 Solid powder, and in stoichiometric ratio n (Li): n (Co): n (Ba): n (Ti): n (Mg): n (Ga) =1.05: 0.7:0.05:0.1:0.1:0.05 weighing the relevant raw material powder, 5% excess Li 2 CO 3 To compensate for Li loss during sintering.
And a second step of: placing the mixed powder in the first step into a corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the tank for ball milling, pouring absolute ethyl alcohol with the volume less than 1/3 of the volume of the ball milling tank and the powder as a solvent, capping the ball milling tank and placing the ball milling tank into a planetary ball mill to obtain the powder, wherein the ball milling speed is 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
And a third step of: and pouring the solution of the ball milling tank in the second step into a beaker, washing the ball milling tank and ball milling beads with absolute ethyl alcohol, pouring the washing solution into a beaker together, then placing the beaker into a blast drying box at 80 ℃ to volatilize all the absolute ethyl alcohol, wherein the process approximately takes 12 hours, and finally pouring the powder mixture dried in the beaker into an agate mortar to grind for about 30 minutes until the powder mixture becomes finer powder without obvious granular feel.
Fourth step: placing the powder mixture after grinding in the third step in a corundum porcelain boat, starting presintering in a muffle furnace, and setting specific sintering conditions as follows: initial temperature of 30℃and 5℃min -1 Is heated to the presintering temperature of 600 ℃ and kept at 600 ℃ for sintering for 4 hours, and finally cooled to the roomAnd (5) taking out the mixture at a temperature.
Fifth step: and (3) grinding the product obtained in the fourth step in an agate mortar for about 30 minutes until the sintered product becomes finer powder without obvious granular feel. Pouring the mixture into a corundum porcelain boat, and sintering again in a muffle furnace, wherein specific sintering conditions are as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to 800 ℃ at the heating rate of the sintering temperature, keeping the temperature of 800 ℃ for 10 hours, cooling to room temperature, and repeatedly grinding and repeatedly sieving to obtain a final product.
Sixth step: mixing the final product obtained in the fifth step with a conductive agent and a binder according to a mass ratio of 8:1:1 uniformly stirring for 24 hours at 500r/min, coating on an aluminum foil, and then drying in an oven at 80 ℃ for 12 hours to obtain the lithium ion battery positive plate of the modified material. Wherein the conductive agent is Super P, and the binder comprises polyvinylidene fluoride.
Seventh step: the positive electrode sheet obtained in the sixth step was transferred into a glove box (in an Ar inert gas atmosphere), and a CR2032 type coin cell was assembled. The negative electrode adopts a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution (EC/EMC/DEC, volume ratio is 1:1:1) and standing for 24h after assembling, and performing electrochemical test.
For LiCo obtained in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobalt oxide modified material is observed by using a field emission scanning electron microscope, the obtained result is shown in figure 1, modified lithium cobalt oxide primary particles with smooth surfaces can be seen, and obvious lamellar stripes can be observed at the edges of the particles.
For LiCo obtained in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobaltate modified material is observed by using a high-resolution transmission electron microscope, the obtained result is shown in fig. 2, and good lattice fringes of the material can be seen, which indicates that the prepared sample has an ordered layered structure.
For LiCo obtained in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 Quaternary doped lithium cobaltate modified material and LiCoO prepared in example 1 2 As can be seen from the graph, the diffraction patterns and LiCoO of the modified lithium cobalt oxide material and the synthesized lithium cobalt oxide material are shown in the graph of FIG. 3 2 The standard diffraction peaks of the standard cards are identical.
The lithium ion battery obtained in example 9 was subjected to cyclic voltammetry, and the results are shown in FIG. 4, from which LiCo 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobalt oxide modified material has two pairs of very obvious oxidation-reduction peaks when being used as a positive electrode material of a lithium ion battery, and corresponds to structural transformation of the internal structure (H1 phase-H2 phase) and the internal structure (H2 phase-H3 phase) of the modified lithium cobalt oxide in the charge and discharge processes of the lithium ion battery respectively. This indicates that the electrochemical performance of the cell is good.
The lithium ion batteries obtained in examples 1 to 9 were subjected to cycle performance test, wherein the results of the cycle performance tests of examples 1, 3, 5, 7, 9 are shown in FIG. 5, liCo obtained in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobaltate modified material has the best performance. Even in the voltage window of 3.0-4.5V, 0.5C (1C=274 mAh.g) -1 ) Under the current density, the initial discharge specific capacity can reach 214 mAh.g -1 After 100 cycles, there was still a capacity retention of 84.47%, indicating LiCo 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobaltate modified material has good stability and higher specific capacity. In addition, the cycle performance of the lithium ion battery assembled in other examples was higher than that of the lithium ion battery assembled in example 1.
The lithium ion batteries obtained in examples 1 to 9 were subjected to rate performance test, liCo obtained in example 9 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The quaternary doped lithium cobaltate modified material has the best performance. The cycle performance test results are shown in fig. 6. At 10.0C(1C＝274mAh·g -1 ) The capacity of the alloy is still kept to be 70 mAh.g under the ultra-high current density of (2) -1 . Even if the current density is recovered to 0.1C, the capacity can be recovered to 190 mAh.g -1 And the sample capacity without modification is only restored to 160 mAh.g -1 。
Experiments can obtain that in Ba, ti, mg, ga quaternary co-doping, liCo 0.7 Ba 0.05 Ti 0.1 Mg 0.1 Ga 0.05 O 2 The performance of the modified lithium cobalt oxide material is optimal.
Compared with the existing preparation methods of some lithium cobaltate modified materials, the high-pressure lithium cobaltate modified material prepared by the method has the advantages of simple preparation steps, less required equipment, short time consumption and excellent multiplying power performance and cycle performance.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. The preparation method of the quaternary doped lithium cobaltate modified material is characterized by comprising the following steps of:
the first step: weighing raw materials Li according to stoichiometric ratio 2 CO 3 、Co 3 O 4 、BaCO 3 、TiO 2 MgO and Ga 2 O 3 Mixing to obtain mixed powder, n (Li) n (Co) n (Ba) n (Mg) n (Ga) =1.05 (0.6-0.98) (0.005-0.1) (0.01-0.1) (0.005-0.1);
and a second step of: taking absolute ethyl alcohol as a solvent, and placing the mixed powder into ball milling equipment for ball milling treatment to obtain a ball milling solution;
and a third step of: mixing the ball milling solution with a washing solution for washing ball milling equipment, volatilizing all absolute ethyl alcohol through heating to obtain a dry powder mixture, and grinding the dry powder mixture to obtain ground powder;
fourth step: presintering the ground powder to obtain a presintering product;
fifth step: and grinding the pre-sintered product, sintering again, and repeatedly grinding and sieving the sintered product to obtain the quaternary doped lithium cobalt oxide modified material.
2. The method for preparing the quaternary doped lithium cobaltate modified material according to claim 1, wherein the second step is specifically: placing mixed powder into corundum ball milling tank, pouring zirconia ball milling beads matched with the ball milling tank into the ball milling tank for ball milling, pouring absolute ethyl alcohol with volume less than 1/3 of the volume of the ball milling tank and less than all mixed powder into the ball milling tank as solvent, capping the ball milling tank, placing the ball milling tank into a planetary ball mill, and stirring at 300 r.min -1 Is ball milled for 10 hours at a rotational rate of (2).
3. The method for preparing a quaternary doped lithium cobaltate modified material according to claim 1, wherein the temperature at which the absolute ethyl alcohol is volatilized in the third step is 80 ℃.
4. The method for preparing a quaternary doped lithium cobaltate modified material according to claim 1, wherein the pre-sintering condition is set as follows: initial temperature of 30℃and 5℃min -1 And (3) heating to the temperature of 600 ℃ of the presintering temperature, keeping the temperature of 600 ℃ and sintering for 4 hours, and finally cooling to room temperature and taking out.
5. The method for preparing a quaternary doped lithium cobaltate modified material according to claim 1, wherein the re-sintering condition is set as follows: initial temperature of 30℃and 5℃min -1 Is heated to 800 ℃ of sintering temperature, kept at 800 ℃ for 10 hours of sintering, and then cooled to room temperature.
6. A quaternary doped lithium cobaltate modified material produced by the production method of any one of claims 1 to 5.
7. The use of the quaternary doped lithium cobaltate modified material of claim 6 in CR2032 type button cells.
8. The use according to claim 7, characterized by the steps of:
1) Mixing the quaternary doped lithium cobaltate modified material with a conductive agent and a binder according to a mass ratio of 8:1:1, uniformly stirring for 24 hours at 500r/min, coating the mixture on an aluminum foil, and drying the mixture at 80 ℃ for 12 hours to obtain a lithium ion battery positive plate of the modified material;
2) And (3) transferring the positive electrode plate of the lithium ion battery into a glove box, and assembling the CR2032 button battery in Ar inert gas atmosphere.
9. The use according to claim 8, wherein the conductive agent is Super P and the binder is polyvinylidene fluoride.
10. The method according to claim 8, wherein in the assembling process in the step 2), the anode is a metal lithium wafer, the diaphragm is Celgard2300, and the electrolyte is 1 mol.L -1 LiPF of (a) 6 Organic solution of LiPF 6 The solvent of the organic solution is EC/EMC/DEC, and the volume ratio is 1:1:1.
CN202310653817.8A 2023-06-02 2023-06-02 Quaternary doped lithium cobaltate modified material and preparation method and application thereof Pending CN117012961A (en)

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