CN112599756A - Fast ion conductor doped coating modified ternary positive electrode material and preparation method thereof - Google Patents

Fast ion conductor doped coating modified ternary positive electrode material and preparation method thereof Download PDF

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CN112599756A
CN112599756A CN202110039662.XA CN202110039662A CN112599756A CN 112599756 A CN112599756 A CN 112599756A CN 202110039662 A CN202110039662 A CN 202110039662A CN 112599756 A CN112599756 A CN 112599756A
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coating
cathode material
ion conductor
preparation
doping
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CN112599756B (en
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夏妮
周友元
朱健
周春仙
葛龙
黄雨晴
刘玮
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Hunan Changyuan Lico Co Ltd
Jinchi Energy Materials Co Ltd
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Hunan Changyuan Lico Co Ltd
Jinchi Energy Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of lithium ion battery material preparation, and provides a fast ion conductor doped coating modified ternary cathode material and a preparation method thereof, which are characterized by comprising the following steps: respectively dissolving the matrix and the doping coating substance in a solvent, and preparing the metal element doping coated lithium ion battery ternary anode material by an electrostatic spinning technology to complete uniform doping coating of the anode material. According to the invention, the metal elements are uniformly doped and coated on the anode material by adopting the electrostatic spinning technology, compared with the existing mechanical solid-phase mixing technology, the damage of a material structure caused by mechanical stress can be relieved, the controllability of the thickness and the type of the coating layer is realized, the coating uniformity is improved, and the doping and coating of the anode material can be completed only by once sintering.

Description

Fast ion conductor doped coating modified ternary positive electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery material preparation, in particular to a fast ion conductor doped coating modified ternary cathode material and a preparation method thereof.
Background
Lithium ion batteries are widely used due to their advantages of high energy density, high voltage, long cycle life, etc., and their use in the commercial automotive industry requires further improvements in energy density and safety, and a key element to meet this challenge is the search for new high capacity electrode materials, particularly positive electrode materials. The LiCoO is synthesized to a certain extent by the nickel-cobalt-manganese ternary positive electrode material with a layered structure2、LiNiO2、LiMnO2The advantages of (2) make up for the deficiencies and improve the material performance.
The capacity of the battery is degraded due to the formation of an insulating material on the surface of an electrode by the side reaction of the battery with air and moisture generated on the surface of the battery during long-term storage and charge/discharge cycles, which reacts with an electrolyte.
Therefore, the direct contact between the active material and the electrolyte can be reduced by coating the coating, the interface stability is improved, the corrosion of the electrolyte to the anode material can be avoided, the structural appearance of the anode material is ensured to be complete, the material capacity attenuation is slowed down, and the excessive consumption of Li + can be reduced when an SEI film is formed.
CN110690435A discloses a fast ion conductor coated high-nickel ternary positive electrode material and a preparation method thereof, wherein the preparation method comprises the steps of adding a high-nickel ternary precursor into a mixed solution, and then stirring, drying and grinding to obtain fast ion conductor coated high-nickel ternary precursor powder. However, the preparation method is long in time consumption, and the precursor is dissociated through high-strength ball milling to damage the morphology of the precursor, so that the structure of the precursor is damaged, the precursor is seriously cracked, and the performance of the anode material is influenced.
CN108807926A discloses a Co/B Co-coated nickel-cobalt-manganese lithium ion positive electrode material and a preparation method thereof, wherein the preparation method comprises the steps of adding the doped element, a nickel-cobalt-manganese precursor and a lithium source compound into a high-speed mixer together for fully mixing, and then calcining to obtain a doped base material; and adding the doped base material into deionized water, uniformly stirring, dropwise adding cobalt salt, continuously stirring to obtain slurry of the positive electrode material coated with the cobalt hydroxide, and mixing with lithium salt for secondary sintering after treatment. However, the method needs secondary sintering, and requires long-time high-temperature calcination for doping modification, which results in increased energy consumption, and moreover, the coating adopts a hydration method, which increases a series of subsequent post-treatments, and has a low capability value in controlling the synthesis uniformity of the material, resulting in uneven element doping coating.
Disclosure of Invention
In order to solve the problems of material structure collapse, long time consumption and uncontrollable doping and coating uniformity caused by the complex preparation method of the lithium ion battery in the prior art, the invention provides a rapid ion conductor doping and coating modified ternary cathode material and a preparation method thereof, and aims to prepare a ternary cathode material which is not damaged and has uniform doping and coating elements.
In a first aspect, the invention provides a preparation method of a fast ion conductor doping coating modified ternary cathode material, which comprises the steps of respectively filling a solution containing a ternary cathode material matrix and a doping coating substance into two injectors of an electrostatic spinning machine, connecting the two injectors by a coaxial needle to form a coaxial structure for electrostatic spinning, preparing a transition metal element doping coated lithium ion battery ternary cathode material, and completing uniform doping coating of the cathode material.
Optionally, the method comprises the following steps:
step S1: preparation of Ni-containing alloyxCoyMn1-x-y (OH)2A precursor, lithium salt and a matrix solution of a conductive high molecular polymer;
step S2: preparing a coating solution containing a transition metal element for doping coating and a conductive high molecular polymer;
step S3: respectively filling the matrix solution and the coating solution into two injectors, mounting coaxial needles, filling the coaxial needles into an electrostatic spinning machine, and spinning after setting electrostatic spinning voltage, receiving distance and injection speed;
step S4: and after spinning is finished, putting a sample obtained by spinning into a tubular furnace for calcining to obtain the fast ion conductor doped coating modified lithium ion battery ternary cathode material.
Optionally, the conductive high molecular polymer in the step S1 and the step S2 is an alcohol, nitrile or ether solvent.
Optionally, the conductive high molecular polymer adopts polyethylene glycol or polyacrylonitrile or a mixture of the polyethylene glycol and the polyacrylonitrile; the concentration of the conductive high molecular polymer is between 5 and 20 percent.
Optionally, in step S3, the coating solution is placed on the inner needle, the matrix solution is placed on the outer needle, the inner diameter of the inner needle of the coaxial needle is 0.3-0.6 mm, and the inner diameter of the outer needle is 1.0-1.8 mm.
Optionally, in the step S3, the electrospinning voltage is set to 10Mpa to 25Mpa, the receiving distance is 8cm to 20cm, and the injection speed is 0.2 mL/h to 0.8 mL/h.
Optionally, the calcination in step S4 is performed at a constant temperature, and the specific calcination temperature is 700-1000 ℃.
Optionally, the calcination in step S4 is performed by using a low-temperature platform calcination, that is, the calcination is performed at a low temperature of 800 ℃ for 3 hours, and then the calcination is performed at a high temperature of 950 ℃ for 12 hours.
Optionally, the transition metal element in step S2 includes at least one or a combination of Zr, Al, Sr, W, La.
In a second aspect, the fast ion conductor doped coating modified ternary cathode material prepared by the preparation method of the fast ion conductor doped coating modified ternary cathode material provided by the invention has a chemical formula of LiNixCoyMn1-x-yO2Wherein y is between 0 and 0.1.
The invention has the beneficial effects that:
1. the solution containing the ternary anode material matrix and the transition metal element is respectively filled into two injectors of an electrostatic spinning machine and connected by a coaxial needle to form a coaxial structure, so that the transition metal element can be uniformly doped and coated on the anode material.
2. The technical scheme of the invention is that Li is reacted with+Transition metal atoms with similar radiuses are integrated and embedded into the ternary cathode material as a dopant, so that the problem of collapse of a layered structure caused by Li/Ni mixed emission can be solved, meanwhile, due to the fact that the valence state of a doped coating element is different from the valence state of lithium, one or more relatively free electrons can appear during doping and coating, charge compensation can occur to keep electrical neutrality, a hole is generated, the generated hole enables the electron to more easily jump from a valence band to a conduction band, and therefore the electron can jump to an empty rail of the conduction band only by consuming a small amount of energy, the conductivity of the material is enhanced, the lithium ion migration is facilitated, the lithium ion conductivity is improved, and the ternary cathode material becomes a high-performance ternary cathode material with a stable structure.
3. According to the preparation method, the coating solution is prepared, so that various elements can be prepared according to different doping coating amounts, the doping coating solution is formed by uniformly stirring, and the controllability of the doping coating element types can be realized; the deposition speed is controlled by adjusting the injection speed of electrostatic spinning, so that the uniform distribution of materials is ensured, samples can not be collected during the acceleration of the spinning speed in order to ensure the uniform distribution of the materials, and the received samples are uniformly distributed after the speed reaches a set speed; the controllability of the thickness of the coating layer is achieved by controlling the injection time.
4. The preparation method is simple, high in speed, low in cost, and uniform and controllable in doping and coating elements, and does not damage the bulk phase and the surface of the material structure.
5. The method adopts a low-temperature and high-temperature platform calcination system, and ensures that the doping and uniform coating of metal elements are realized after the lithium infiltration is fully completed.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
Fig. 1a is an SEM image of the cathode material prepared in comparative example 1;
FIG. 1b is an SEM image of a ternary cathode material prepared in example 1 of the present application;
FIG. 1c is an SEM image of a ternary cathode material prepared in example 2 of the present application;
fig. 2a is a TEM image of the cathode material prepared in comparative example 1;
FIG. 2b is a TEM image of the ternary cathode material prepared in example 1 of the present application;
FIG. 2c is a TEM image of the ternary cathode material prepared in example 2 of the present application;
fig. 3 is a graph showing the results of capacity retention of the positive electrode materials prepared in comparative example 1, and example 2 of the present application.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
The ternary positive electrode materials prepared in comparative example 1, example 1 and example 2 of the present application were all LiNixCo0.05Mn0.95-xO2The doped and coated substance is nano oxide of Zr, La and Al.
The mass ratio of each substance described in the present application is the mass ratio of the substance to NixCo0.05Mn0.95-x (OH)2Mass ratio of the precursor.
Comparative example 1
Comparative example 1 discloses the preparation of fast ion conductor doped coated LiNi by the conventional solid phase methodXCo0.05Mn0.95-XO2The preparation method of the ternary cathode material comprises the following steps:
mixing NixCo0.05Mn0.95-x (OH)2Precursor, lithium salt and nano ZrO2Mixing in a high-speed ball mill mixer at a mass ratio of 0.35%, calcining at 950 deg.C for 12h in a temperature programmed tube furnace at a temperature rise rate of 5 deg.C/min to obtain a first-calcined material, a second-calcined material and 0.1% nano La2O3And 0.2% by mass of nano Al2O3Uniformly mixing, calcining at 450 ℃ for 5h, and cooling to room temperature to obtain LiNi doped and coated with Zr, Al and LaxCo0.05Mn0.95-xO2A ternary positive electrode material.
Example 1
Embodiment 1 discloses a preparation method of a fast ion conductor doped coating modified ternary cathode material, which comprises the following steps:
mixing NixCo0.05Mn0.95-x (OH)2Dissolving the precursor, lithium salt and polyethylene glycol with the concentration of 12% in N, N-dimethylformamide solvent, stirring uniformly, and packagingPutting into a No. 1 syringe; nano ZrO in an amount of 0.35 mass%20.1% by mass of nano La2O30.2% by mass of nano Al2O3Dissolving polyethylene glycol with concentration of 12% in N, N-dimethylformamide solvent, stirring, and placing into No. 2 syringe; installing coaxial needles on the No. 1 injector and the No. 2 injector, then installing the No. 1 injector and the No. 2 injector into an electrostatic spinning machine, setting electrostatic spinning voltage to be 18 Mpa, receiving distance to be 15 cm, and injection speed to be 0.3 mL/h, and then starting spinning; and after spinning is finished, putting a sample obtained by spinning into a temperature programming tube furnace, calcining for 12h at 950 ℃, wherein the heating rate is 5 ℃/min, and cooling to room temperature after calcining is finished to obtain the fast ion conductor doped and uniformly coated ternary cathode material.
Example 2
Example 2 differs from example 1 only in that the injection rate is increased to 0.6 mL/h.
Mixing NixCo0.05Mn0.95-x (OH)2Dissolving the precursor, lithium salt and polyethylene glycol with the concentration of 12% in an N, N-dimethylformamide solvent, uniformly stirring, and filling into a No. 1 syringe; nano ZrO in an amount of 0.35 mass%20.1% by mass of nano La2O30.2% by mass of nano Al2O3Dissolving polyethylene glycol with concentration of 12% in N, N-dimethylformamide solvent, stirring, and placing into No. 2 syringe; installing coaxial needles on the No. 1 injector and the No. 2 injector, then installing the No. 1 injector and the No. 2 injector into an electrostatic spinning machine, setting electrostatic spinning voltage to be 18 Mpa, receiving distance to be 15 cm and injection speed to be 0.6 mL/h, and then starting spinning; and after spinning is finished, putting a sample obtained by spinning into a temperature programming tube furnace, calcining for 12h at 950 ℃, wherein the heating rate is 5 ℃/min, and cooling to room temperature after calcining is finished to obtain the fast ion conductor doped and uniformly coated ternary cathode material.
Example 3
Example 3 is different from example 1 only in that the doping coating solution charged into syringe No. 2 is composed of nano ZrO in an amount of 0.35% by mass20.15% by mass of nano WO30.2% by mass of nano Al2O3And polyethylene glycol with the concentration of 12 percent is dissolved in N, N-dimethylformamide solvent.
Example 4
Example 4 is different from example 1 only in that the doping coating solution charged into syringe No. 2 is composed of nano ZrO in an amount of 0.35% by mass20.15 percent of nano SrO and 0.2 percent of nano Al by mass2O3And polyethylene glycol with the concentration of 12 percent is dissolved in N, N-dimethylformamide solvent.
Example 5
Example 5 is different from example 1 only in that the electroconductive high molecular polymer is polyacrylonitrile at a concentration of 20%.
Example 6
Example 6 is different from example 1 only in that the conductive high molecular polymer is polyacrylonitrile at a concentration of 5% and polyethylene glycol at a concentration of 20%.
Example 7
Example 7 differs from example 1 only in that the inner diameter of the coaxial needle is 0.3 mm and the inner diameter of the outer needle is 1.0 mm.
Example 8
Example 8 compared to example 1, the only difference was that the inner diameter of the coaxial needle was 0.6 mm and the outer diameter was 1.8 mm.
Example 9
Example 9 differs from example 1 only in that the parameters of electrospinning are: the electrostatic spinning voltage is 10Mpa, the receiving distance is 8cm, and the injection speed is 0.2 mL/h.
Example 10
Example 10 differs from example 1 only in that the parameters of electrospinning are: the electrostatic spinning voltage is 25Mpa, the receiving distance is 20cm, and the injection speed is 0.8 mL/h.
Example 11
Example 11 is different from example 1 only in that after spinning, the sample obtained by spinning is put into a temperature programmed tube furnace, and is firstly insulated at a low temperature of 800 ℃ for 3 hours and then calcined at a high temperature of 950 ℃ for 12 hours.
Example 12
Example 12 compares with example 1, the difference is only that after the spinning is finished, the sample obtained by spinning is put into a temperature-programmed tube furnace to be calcined for 12 hours at 700 ℃.
Example 13
Example 13 compares with example 1, the difference is that after spinning is completed, the sample obtained by spinning is put into a temperature programmed tube furnace to be calcined for 12 hours at 1000 ℃.
The materials produced in the above comparative examples and examples were analyzed.
Material mapping analysis:
the ternary positive electrode materials prepared in comparative example 1, example 1 and example 2 were subjected to electron microscopy analysis, respectively.
Fig. 1a is an SEM image of the cathode material prepared in comparative example 1; FIG. 1b is an SEM image of a ternary cathode material prepared in example 1 of the present application; fig. 1c is an SEM image of the ternary cathode material prepared in example 2 of the present application. As can be seen from fig. 1b, the positive electrode material prepared in example 1 has no apparent point-like substances on the surface. The preparation method adopted in the comparative example 1 has a serious damage degree to the materials, while the preparation method of the example 1 has almost no damage to the materials, well maintains the structure of the materials and is beneficial to improving the cycle performance of the materials.
Fig. 2a is a TEM image of the cathode material prepared in comparative example 1; FIG. 2b is a TEM image of the ternary cathode material prepared in example 1 of the present application; fig. 2c is a TEM image of the ternary cathode material prepared in example 2 of the present application. As can be seen from fig. 2b, the coating substance on the surface of the cathode material (see fig. 2 b) prepared in example 1 is uniform and has no aggregation phenomenon; on the other hand, the positive electrode material prepared in example 2 (see fig. 2 c) has a larger concentration of coating due to the increased injection speed, but the coating layer is thinner than the positive electrode material prepared in comparative example 1 (see fig. 2 a), so the coating effect is better than that of comparative example 1.
And (3) electricity buckling preparation:
the three-element positive electrode materials prepared in comparative example 1, example 1 and example 2 are respectively used as positive electrode materials of lithium ion batteries, and a lithium sheet is used as a negative electrode material to prepare the CR2025 button cell, and the preparation process comprises the following steps: dissolving a positive electrode material, carbon black and polytetrafluoroethylene in N-methyl pyrrolidone according to a proper proportion, fully grinding, coating on an aluminum foil, drying, knocking a sheet, and sequentially completing assembly in a glove box by the sequence of a positive electrode shell → a positive electrode sheet → a diaphragm → a lithium sheet → a gasket → a negative electrode shell, and respectively naming the prepared batteries as a battery A, a battery B and a battery C.
And (3) analyzing the battery performance:
and respectively carrying out constant-current charge and discharge performance tests on the battery A, the battery B and the battery C on a battery test system. Fig. 3 is a graph showing the results of capacity retention of the positive electrode materials prepared in comparative example 1, and example 2 of the present application. Wherein, the abscissa Cycle Number represents the Number of cycles, and the ordinate Capacity Retention represents the Capacity Retention rate. As can be seen from fig. 3, the cycle performance of battery B is significantly improved, which indicates that the structure of the positive electrode material prepared in example 1 remains intact, and structural collapse does not occur, resulting in cycle performance degradation; meanwhile, the coating layer of the cathode material prepared in the embodiment 1 is uniform, and the corrosion of the electrolyte to the cathode material is well prevented.
The ternary cathode material prepared in the embodiment 3 is assembled into a buckle according to the method for preparing the buckle, the electrochemical performance of the ternary cathode material is tested, the first discharge capacity and the first effect of the material can be improved because the doping coating of the W element can refine the size of primary particles, the first discharge capacity of the cathode material in the embodiment 1 is 190mAh/g, the first effect is 88.3%, the first discharge capacity of the cathode material in the embodiment 3 is 192mAh/g, and the first effect is 88.9%, but the cycle performance of the material is accelerated.
The ternary cathode material prepared in the embodiment 4 is assembled into a buckle according to the method for preparing the buckle, the electrochemical performance of the buckle is tested, Sr has an effect of assisting melting, the growth of the ternary cathode material can be promoted once by doping the ternary cathode material, the increase of primary particles can influence the capacity, the compaction density of the ternary cathode material can be improved, meanwhile, Sr can inhibit the gas generation of a battery, and the cycle performance is improved, the first discharge capacity of the ternary cathode material in the embodiment 4 is 185mAh/g, and the first effect is 87.6%.
Unless specifically stated otherwise, the numerical values set forth in these examples do not limit the scope of the invention. In all examples shown and described herein, unless otherwise specified, any particular value should be construed as merely illustrative, and not restrictive, and thus other examples of example embodiments may have different values.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.

Claims (10)

1. A preparation method of a ternary anode material modified by doping and coating a fast ion conductor is characterized in that a solution containing a ternary anode material matrix and a doping coating substance is respectively filled into two injectors of an electrostatic spinning machine and connected by coaxial needles to form a coaxial structure for electrostatic spinning, so that the ternary anode material of a lithium ion battery coated by doping transition metal elements is prepared, and uniform doping and coating of the anode material are completed.
2. The preparation method of the fast ion conductor doped coating modified ternary cathode material according to claim 1, characterized by comprising the following steps:
step S1: preparation of Ni-containing alloyxCoyMn1-x-y (OH)2A precursor, lithium salt and a matrix solution of a conductive high molecular polymer;
step S2: preparing a coating solution containing a transition metal element for doping coating and a conductive high molecular polymer;
step S3: respectively filling the matrix solution and the coating solution into two injectors, mounting coaxial needles, filling the coaxial needles into an electrostatic spinning machine, and spinning after setting electrostatic spinning voltage, receiving distance and injection speed;
step S4: and after spinning is finished, putting a sample obtained by spinning into a tubular furnace for calcining to obtain the fast ion conductor doped coating modified lithium ion battery ternary cathode material.
3. The method for preparing the ternary cathode material modified by doping and coating of the fast ion conductor according to claim 2, wherein the conductive high molecular polymer in the step S1 and the step S2 is an alcohol, nitrile or ether solvent.
4. The preparation method of the fast ion conductor doped coating modified ternary cathode material according to claim 3, wherein the conductive high molecular polymer is polyethylene glycol or polyacrylonitrile or a mixture of the polyethylene glycol and the polyacrylonitrile; the concentration of the conductive high molecular polymer is between 5 and 20 percent.
5. The method for preparing the ternary cathode material with the modified fast ion conductor doped coating according to claim 2, wherein in step S3, the coating solution is placed on an inner needle, the matrix solution is placed on an outer needle, and the inner diameter of the inner needle of the coaxial needle is 0.3-0.6 mm and the inner diameter of the outer needle is 1.0-1.8 mm.
6. The preparation method of the ternary cathode material doped and coated with the fast ion conductor and modified according to claim 2, wherein in the step S3, the electrostatic spinning voltage is set to 10 MPa-25 MPa, the receiving distance is 8-20 cm, and the injection speed is 0.2-0.8 mL/h.
7. The method for preparing the ternary cathode material doped and coated with the modified fast ion conductor according to claim 2, wherein the calcination in the step S4 is performed at a constant temperature, and the specific calcination temperature is 700-1000 ℃.
8. The method for preparing the ternary cathode material doped and coated with the modified fast ion conductor according to claim 2, wherein the calcination in the step S4 is performed by using a low-temperature platform calcination, i.e., firstly performing low-temperature heat preservation at 800 ℃ for 3 hours, and then performing high-temperature calcination at 950 ℃ for 12 hours.
9. The method as claimed in claim 2, wherein the transition metal element in step S2 comprises at least one or more of Zr, Al, Sr, W, La.
10. The fast ion conductor doped coating modified ternary cathode material prepared by the preparation method of the fast ion conductor doped coating modified ternary cathode material according to any one of claims 1 to 9, wherein the chemical formula of the ternary cathode material is LiNixCoyMn1-x-yO2Wherein y is between 0 and 0.1.
CN202110039662.XA 2021-01-13 2021-01-13 Fast ion conductor doped coating modified ternary positive electrode material and preparation method thereof Active CN112599756B (en)

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