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CN118899408A - Preparation method of composite positive electrode material - Google Patents

Preparation method of composite positive electrode material Download PDF

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Publication number
CN118899408A
CN118899408A CN202310495188.0A CN202310495188A CN118899408A CN 118899408 A CN118899408 A CN 118899408A CN 202310495188 A CN202310495188 A CN 202310495188A CN 118899408 A CN118899408 A CN 118899408A
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positive electrode
solid electrolyte
electrode material
mixing
manganese compound
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Inventor
何定德
谢瀚纬
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Advanced Lithium Electrochemistry Co Ltd
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Advanced Lithium Electrochemistry 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/52—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (Mn2O4)2-, e.g. Li2(NixMn2-x)O4 or Li2(MyNixMn2-x-y)O4
    • 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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
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    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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  • Composite Materials (AREA)
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Abstract

A preparation method of a composite positive electrode material comprises the following steps: (a) Providing a nickel-manganese compound material, wherein the nickel-manganese compound material is Ni xMny(OH)2 or Ni xMny O, and x+y=1; (b) Providing a solid electrolyte material, and mechanically mixing the nickel-manganese compound material and the solid electrolyte material into a composite material, wherein the solid electrolyte material has a weight percentage relative to the nickel-manganese compound material, and the weight percentage ranges from 0.2wt.% to 1.0 wt.%; and (c) providing a lithium source, mixing the lithium source and the composite material, and sintering to form the composite positive electrode material, wherein the composite positive electrode material comprises a core layer and a coating layer, the core layer is composed of LiNi 2xMn2yO4, the coating layer coats the core layer, and the coating layer is composed of a solid electrolyte material.

Description

Preparation method of composite positive electrode material
Technical Field
The invention relates to a positive electrode material of a secondary battery, in particular to a preparation method of a composite positive electrode material, which utilizes a dry mechanical mixing mode to treat a precursor and a solid electrolyte, synchronously completes the surface coating of the solid electrolyte when the positive electrode material is formed, has simple and quick process and can effectively improve the performance of the positive electrode material.
Background
In recent years, the performance requirements of electric vehicles and energy storage devices have been gradually increased, and secondary batteries applied thereto are also required to have good performance. Among the many battery types, lithium manganese nickel oxide/spinel (LiMn 1.5Ni0.5O4, LNMO) is a positive electrode material that can be charged at high voltage (5V). Due to the high potential, lithium manganese nickel oxide/spinel materials have a higher energy density than lithium cobalt oxide and lithium iron phosphate. Thus, a battery based on LMNO can be used for high energy and high rate applications.
However, the capacity of LMNO is decomposed by the electrolyte at high voltage, which is liable to cause problems such as capacity exertion, rate performance and cycle life deterioration. Thus, surface modification of LMNO has become an important issue. The traditional mode of using the LMNO combined with the solid electrolyte is to coat the solid electrolyte on the LMNO material so as to improve the microstructure of the surface of the LMNO, thereby forming a frame surface which can conduct ions and is conductive on the surface of the LMNO, effectively relieving the problem of poor circulation of the LMNO under high pressure and improving the conductivity of the LMNO. However, conventional LMNO coating of solid state electrolytes requires complicated procedures and may detract from the performance of LMNO during coating of solid state electrolytes.
In view of the foregoing, it is desirable to provide a method for preparing a composite positive electrode material. The precursor and the solid electrolyte are processed by dry mechanical mixing, so that the surface coating of the solid electrolyte is completed synchronously when the positive electrode material is formed, the process is simple and quick, the performance of the positive electrode material can be effectively improved, and the defects in the prior art are overcome.
Disclosure of Invention
The invention aims to provide a preparation method of a composite positive electrode material, which utilizes a mixing mode of a dry mechanical fusion method (mechanofusion) to treat a precursor and a solid electrolyte, synchronously completes the surface coating of the solid electrolyte when the positive electrode material is formed, has simple and quick process and can effectively improve the performance of the positive electrode material. Aiming at the application of lithium nickel manganese oxide anode material LMNO coated lithium aluminum titanium phosphate (Li 1.3Al0.3Ti1.7(PO4)3, LATP) solid electrolyte, the invention utilizes a dry mechanical mixing method to mix nickel manganese compound material of Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O with the solid electrolyte material, then adds a lithium source to mix and sinter the mixture to form the composite anode material with a core layer and a coating layer. The inner core layer is composed of LiNi 0.5Mn1.5O4 and the outer cladding layer is composed of a solid electrolyte material. Because the Lithium Aluminum Titanium Phosphate (LATP) solid electrolyte has good ionic conductivity, when the Lithium Aluminum Titanium Phosphate (LATP) is coated on the surface of the lithium nickel manganese oxide anode material LMNO to form a composite anode material, the lithium nickel manganese oxide anode material LMNO can be helped to improve the multiplying power performance and the cycle performance, wherein the Lithium Aluminum Titanium Phosphate (LATP) coating layer can also provide a protective effect to slow down the influence of the damage of the surface of the material by electrolyte. Furthermore, to obtain an optimal coating effect of the solid electrolyte, the weight percentage of the solid electrolyte material relative to the nickel-manganese compound material such as Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O is more preferably controlled between 0.2wt.% and 1.0wt.%, and more preferably between 0.2wt.% and 0.3 wt.%. The invention can form the coating layer for improving the multiplying power performance of the lithium nickel manganese oxide anode material LMNO only by adding a small amount of lithium aluminum titanium phosphate LATP solid electrolyte, and further reduces the manufacturing cost.
The invention further aims at providing a preparation method of the composite anode material. Compared with the method that Lithium Aluminum Titanium Phosphate (LATP) is directly used for coating the lithium nickel manganese oxide anode material LMNO, the method of mixing the lithium titanium aluminum titanium phosphate (LATP) into the pretreatment material of the lithium nickel manganese oxide anode material LMNO in a mechanical mode such as a mechanical fusion method (Mechanofusion method) and synthesizing the lithium nickel manganese oxide anode material LMNO is further used for reducing the generation of Mn 3+, avoiding the dissolution of Mn 3+ in the anode material and the reduction and deposition of Mn 3+ in the cathode, and causing the deterioration of cycle electrical property. The working temperature of the mixing process is, for example, between 25 ℃ and 45 ℃ and the processing is carried out stepwise for 5 minutes to 30 minutes at a rotational speed in the range 700rpm to 3500 rpm. By controlling the mode, working temperature, rotation speed and time of mixing Lithium Aluminum Titanium Phosphate (LATP) with the pretreatment material, the structural defect of the solid electrolyte coating layer caused by high temperature and excessive friction among particles can be prevented, and meanwhile, the lithium nickel manganese oxide anode material LMNO can exert low impedance and good charge and discharge performance through the coating layer of the LATP solid electrolyte.
In order to achieve the above object, the present invention provides a method for preparing a composite positive electrode material, comprising the steps of: (a) Providing a nickel-manganese compound material, wherein the nickel-manganese compound material is Ni xMny(OH)2 or Ni xMny O, and x+y=1; (b) Providing a solid electrolyte material, and mechanically mixing the nickel-manganese compound material and the solid electrolyte material into a composite material, wherein the solid electrolyte material has a weight percentage relative to the nickel-manganese compound material, and the weight percentage ranges from 0.2wt.% to 1.0 wt.%; and (c) providing a lithium source, mixing the lithium source and the composite material, and sintering to form the composite positive electrode material, wherein the composite positive electrode material comprises a core layer and a coating layer, the core layer is composed of LiNi 2xMn2yO4, the coating layer coats the core layer, and the coating layer is composed of a solid electrolyte material.
In one embodiment, the nickel manganese compound material is Ni 0.25Mn0.75(OH)2, and the mechanical mixing step (b) includes a first heat treatment process, wherein the first heat treatment temperature is 300 ℃ to 850 ℃, the treatment time of the first heat treatment process is 5 hours to 7 hours, and the temperature rising rate of the first heat treatment process is 2.5 ℃/min.
In one embodiment, the nickel manganese compound material is Ni 0.25Mn0.75 O, and the step (a) includes a pre-oxidation process, wherein the temperature of the pre-oxidation process is 300 ℃ to 850 ℃, the treatment time of the pre-oxidation process is 5 hours to 7 hours, and the temperature rising rate of the pre-oxidation process is 2.5 ℃/min.
In one embodiment, the step (b) further comprises a first heat treatment process after the mechanical mixing, wherein the temperature of the first heat treatment process is in a range of 300 ℃ to 750 ℃, the treatment time of the first heat treatment process is 5 hours to 7 hours, and the temperature rising rate of the first heat treatment process is 2.5 ℃/min.
In one embodiment, mechanically mixing the nickel manganese compound material and the solid electrolyte in step (b) comprises mixing at 700rpm for 5 minutes, at 1400rpm for 5 minutes, at 2100rpm for 5 minutes, at 2800rpm for 10 minutes, and at 3500rpm for 10 minutes.
In one embodiment, the working temperature of mechanically mixing the nickel manganese compound material and the solid electrolyte in step (b) is between 25 ℃ and 45 ℃.
In one embodiment, the solid electrolyte has the chemical formula Li 1+zAlzTi2-z(PO4)3, and z+.2.
In one embodiment, the mechanical means comprises a mechanical fusion process.
In one embodiment, step (c) comprises mechanically mixing the lithium source and the composite material for 5 minutes at 700rpm and for 30 minutes at 1400 rpm.
In one embodiment, the step (c) includes a second heat treatment process having a temperature ranging from 300 ℃ to 710 ℃ and a treatment time of 24 hours to 30 hours, wherein the second heat treatment process has a temperature rise rate of 2.5 ℃/min.
In one embodiment, the nickel manganese compound material in the composite material of step (c) has a molar ratio of 1:1.02 relative to the lithium source.
In one embodiment, the weight percent ranges from 0.2wt.% to 0.3 wt.%.
In one embodiment, the nickel manganese compound material has an average particle size ranging from 10 microns to 20 microns and the solid electrolyte material has an average particle size ranging from 1 micron to 5 microns.
Drawings
FIG. 1 is a schematic diagram of a positive electrode material according to an embodiment of the invention.
FIG. 2A is an SEM image of a Ni 0.25Mn0.75(OH)2 nickel manganese compound material of the present invention.
FIG. 2B is an SEM image of a Ni-Mn compound material of Ni 0.25Mn0.75 O according to the present invention.
FIG. 2C is an SEM image of lithium aluminum phosphate (LATP) of the present invention.
FIG. 3 is a flow chart of a method for preparing a composite positive electrode material according to a first embodiment of the present invention.
Fig. 4A to 4D are SEM images of the positive electrode material of the first comparative example.
Fig. 5A to 5D are SEM images of a positive electrode material according to a first example of the present invention.
Fig. 6A to 6D are SEM images of a positive electrode material according to a second example of the present invention.
Fig. 7A to 7D are SEM images of a positive electrode material according to a third exemplary embodiment of the present invention.
Fig. 8 is a graph showing charge and discharge of potential-capacitance values of a first example, a second example, and a third example of the present invention.
Fig. 9 is a graph showing the capacity retention rate versus cycle number discharge of the first, second, and third examples of the present invention.
FIG. 10 is a flow chart of a method for preparing a composite positive electrode material according to a second embodiment of the present invention.
Fig. 11A to 11D are SEM images of a positive electrode material according to a fourth example of the present invention.
Fig. 12A to 12D are SEM images of a positive electrode material according to a fifth exemplary embodiment of the present invention.
Fig. 13A to 13D are SEM images of a positive electrode material according to a sixth exemplary embodiment of the present invention.
Fig. 14 is a graph showing charge and discharge of potential-capacitance values of a first comparative example, a fourth example, a fifth example, and a sixth example according to the present invention.
Fig. 15 is a graph showing the capacity retention rate versus cycle number discharge of the first comparative example, the fourth example, the fifth example, and the sixth example according to the present invention.
Fig. 16 is a graph showing charge and discharge curves of potential-capacitance values of the second and third comparative examples and the first and fourth examples of the present invention.
Fig. 17 is a graph showing the discharge rate of the third comparative example and the discharge rate of the fourth example according to the first and fourth examples of the present invention.
Detailed Description
Some exemplary embodiments embodying features and advantages of the present invention will be described in detail in the following description. It will be understood that the invention is capable of various modifications in its various aspects, all without departing from the scope of the invention, and that the description and drawings are intended to be illustrative in nature and not as limiting. For example, the following description of the invention includes embodiments in which a first feature is disposed on or over a second feature, including embodiments in which the first feature is disposed in direct contact with the second feature, as well as embodiments in which additional features may be disposed between the first feature and the second feature, such that the first feature and the second feature may not be in direct contact. In addition, it should be understood that although the terms "first," "second," "third," etc. may be used in the claims to describe various elements, these elements should not be limited by these terms, and that these elements described in the embodiments are represented by different reference numerals. These terms are intended to be used as separate components, for example: the first component may be referred to as a second component. Likewise, a second component may also be referred to as a first component without departing from the scope of the embodiments. The term "and/or" in the specification includes any and all combinations of one or more of the associated listed items. The term "about" refers to an average value within standard error limits recognized by those of ordinary skill in the art to be acceptable. All numerical ranges, amounts, values, and percentages disclosed herein (e.g., angle, length of time, temperature, operating conditions, ratio of amounts, etc.) should be understood to be modified by the term "about" or "substantially" in all embodiments, unless explicitly stated otherwise in the operating/working examples. Accordingly, unless indicated otherwise, the numerical parameters set forth in the present disclosure and attached claims are approximations that may vary as desired. For example, the significance of each numerical parameter should be construed in light of at least the application of ordinary rounding techniques. Ranges can be expressed herein as from one endpoint to the other endpoint, or between two endpoints. Unless otherwise indicated, all ranges disclosed herein are inclusive of the endpoints.
FIG. 1 is a schematic diagram of a composite positive electrode material according to an embodiment of the invention. In this embodiment, the composite cathode material 1 includes a core layer 10 and a coating layer 20 coating the core layer 10. The core layer 10 is composed of a lithium nickel manganese oxide positive electrode material LMNO, wherein the composition of the lithium nickel manganese oxide positive electrode material LMNO is LiNi 0.5Mn1.5O4. The coating layer 20 is composed of lithium aluminum phosphate (Li 1.3Al0.3Ti1.7(PO4)3, LATP). In this embodiment, the lithium nickel manganese oxide positive electrode material LMNO is a high-voltage positive electrode material containing no cobalt element, and has a higher oxidation-reduction potential and energy density. The composite positive electrode material 1 may be used in a liquid electrolyte 30, and li+ ions 11 may be inserted into or extracted from the lithium nickel manganese oxide positive electrode material LMNO of the inner core layer 10 through a coating layer 20 formed of a solid electrolyte. The composite positive electrode material 1 of the present invention is formed by mechanically mixing Lithium Aluminum Titanium Phosphate (LATP) into a pretreatment material of lithium nickel manganese oxide positive electrode material LMNO, for example, by a mechanical fusion method (Mechanofusion method), and synthesizing lithium nickel manganese oxide positive electrode material LMNO. The pretreatment material may be, for example, ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O nickel manganese compound material, and is not directly coated with lithium nickel manganese oxide anode material LMNO. FIG. 2A is an SEM image of a Ni 0.25Mn0.75(OH)2 nickel manganese compound material of the present invention. FIG. 2B is an SEM image of a nickel manganese compound material of the present invention NiMnO. FIG. 2C is an SEM image of lithium aluminum phosphate (LATP) of the present invention. Of course, the type, composition ratio and material characteristics of the core layer 10 and the coating core layer 10 of the composite anode material 1 of the present invention can be adjusted according to the practical application requirements, and are not limited thereto. The method for preparing the composite cathode material 1 according to the present invention, in which the precursor and the solid electrolyte are treated by a dry mechanical fusion method (Mechanofusion method) in a mixed manner, will be described below.
FIG. 3 is a flow chart of a method for preparing a composite positive electrode material according to a first embodiment of the present invention. In this embodiment, a nickel-manganese compound material is provided first, wherein the nickel-manganese compound material is Ni 0.25Mn0.75(OH)2, as shown in step S01. The Ni 0.25Mn0.75(OH)2 nickel manganese compound material has an average particle size in the range of 10 microns to 20 microns, for example 12.90 microns, with a surface area of 0.6m 2/g. In addition, lithium aluminum titanium phosphate LATP solid electrolyte materials are provided, the solid electrolyte materials having an average particle size in the range of 1 micron to 5 microns, such as 1.79 microns. And the Ni 0.25Mn0.75(OH)2 nickel manganese compound material and the LATP solid electrolyte material are mechanically mixed into a composite material as shown in step S02. Wherein the LATP solid electrolyte material has a weight percentage with respect to the Ni 0.25Mn0.75(OH)2 nickel manganese compound material, the weight percentage ranging between 0.2wt.% and 1.0 wt.%. In this embodiment, the mechanical means is more referred to as dry mechanical fusion (Mechanofusion method). Wherein mechanically mixing the nickel manganese compound material and the solid electrolyte in step S02 comprises mixing at 700rpm for 5 minutes, at 1400rpm for 5 minutes, at 2100rpm for 5 minutes, at 2800rpm for 10 minutes, and at 3500rpm for 10 minutes. The working temperature of mechanically mixing nickel manganese compound material and solid electrolyte is between 25 ℃ and 45 ℃. After the mechanical mixing, a first heat treatment process is performed, as shown in step S03. Wherein the first heat treatment temperature ranges from 300 ℃ to 850 ℃, the treatment time of the first heat treatment program ranges from 5 hours to 7 hours, and the heating rate of the first heat treatment program is 2.5 ℃/min.
Next, as shown in step S04, a lithium source, such as lithium hydroxide, is provided, and the lithium source and the aforementioned composite material are mixed and sintered to form a composite positive electrode material. The Ni 0.25Mn0.75(OH)2 nickel manganese compound material in the composite material has a mole ratio of 1:1.02 relative to the lithium source. Wherein the sintering in step S04 is a second heat treatment process, the temperature of the second heat treatment process ranges from 300 ℃ to 710 ℃, the treatment time of the second heat treatment process ranges from 24 hours to 30 hours, and the heating rate of the second heat treatment process is 2.5 ℃/min. The composite positive electrode material 1, as shown in fig. 1, comprises a core layer 10 and a coating layer 20, wherein the core layer 10 is made of LiNi 0.5Mn1.5O4, the coating layer 20 coats the core layer 10, and the coating layer 20 is made of LATP solid electrolyte material.
It is noted that, in this embodiment, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75(OH)2 nickel manganese compound material is more controlled between 0.2wt.% and 1.0wt.% for the best coating effect.
Fig. 4A to 4D disclose SEM images of the first comparative example. In the first comparative example, lithium nickel manganese oxide positive electrode material LMNO (LiNi 0.5Mn1.5O4) was not coated with LATP solid electrolyte.
Fig. 5A to 5D are SEM images of a composite cathode material according to a first exemplary embodiment of the present invention. In the first example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75(OH)2 nickel manganese compound material is 0.2wt.%, and the composite cathode material is prepared through the foregoing steps S01 to S04.
Fig. 6A to 6D are SEM images of a composite cathode material according to a second exemplary embodiment of the present invention. In the second example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75(OH)2 nickel manganese compound material is 0.5wt.%, and the composite cathode material is prepared by the steps S01 to S04.
Fig. 7A to 7D are SEM images of a composite cathode material according to a third exemplary embodiment of the present invention. In a third example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75(OH)2 nickel manganese compound material is 1.0wt.%, and the composite cathode material is prepared through the foregoing steps S01 to S04.
Fig. 8 is a graph showing charge and discharge of potential-capacitance values of a first example, a second example, and a third example of the present invention. The button cell manufactured by the first comparative example, the first example, the second example and the third example of the present invention was tested at a charge-discharge rate (C-rate) of 0.1C. The positive electrode plate of button cell is made of positive electrode material, conductive agent and adhesive in the ratio of 94:4:2, and the negative electrode plate is lithium metal. The electrolyte of the button cell included 1.15M lithium hexafluorophosphate (LiPF 6), ethylene carbonate (Ethylene carbonate, EC), diethyl carbonate (Diethyl carbonate, DEC), ethylmethyl carbonate (ETHYL METHYL Carbonate, EMC) and 5wt% fluoroethylene carbonate (Fluoroethylene carbonate, FEC). Wherein the charge-discharge capacity results of the first and second turns at 0.1C are shown in Table I. In addition, the results of the first comparative example and the first, second and third examples of the present invention are shown in Table I, wherein the samples were charged at 0.2 and then discharged at 1C/2C/3C/5C. As shown in fig. 8 and table one, the first, second and third examples of the present invention all have better capacitance performance and rate performance than those of the first comparative example. Therefore, the invention utilizes a dry mechanical mixing method to mix Ni 0.25Mn0.75(OH)2 nickel manganese compound material and LATP solid electrolyte material, then adds a lithium source to mix and sinter, thus forming the composite anode material with a core layer and a coating layer, and being capable of helping to improve the capacitance performance and the multiplying power performance of the lithium nickel manganese oxide anode material LMNO.
List one
FIG. 9 is a graph showing the capacity retention rate versus cycle number discharge for the first, second, and third examples of the present invention. The button cell manufactured by the first, second and third examples of the present invention was tested at a 1C charge-discharge rate (C-rate). As shown in fig. 9, the capacitance storage ratios of the first example to the third example of the present invention are all superior to those of the first comparative example. Therefore, the composite positive electrode material formed by the preparation method can help to improve the cycle performance of the lithium nickel manganese oxide positive electrode material LMNO and prolong the cycle life.
FIG. 10 is a flow chart of a method for preparing a composite positive electrode material according to a second embodiment of the present invention. In this embodiment, a nickel-manganese compound material is provided first, wherein the nickel-manganese compound material is Ni 0.25Mn0.75 O, as shown in step S01'. In this embodiment, ni 0.25Mn0.75 O is further prepared by treating Ni 0.25Mn0.75(OH)2 with a pre-oxidation process. As shown in step S00', ni 0.25Mn0.75(OH)2 is subjected to a pre-oxidation process to obtain Ni 0.25Mn0.75O.Ni0.25Mn0.75 O nickel manganese compound material with an average particle size ranging from 10 microns to 20 microns, for example 13.96 microns, and a surface area of 20.49m 2/g. Wherein the temperature of the pre-oxidation procedure is in the range of 300 ℃ to 850 ℃, the treatment time of the pre-oxidation procedure is 5 hours to 7 hours, and the temperature rising rate of the pre-oxidation procedure is 2.5 ℃/min. Of course, in other embodiments, ni 0.25Mn0.75 O may be obtained by other processing procedures, and the invention is not limited thereto. Next, as shown in step S02', a lithium aluminum titanium phosphate LATP solid electrolyte material is provided, and the Ni 0.25Mn0.75 O nickel manganese compound material and the LATP solid electrolyte material are mixed into a composite material by a dry mechanical fusion method (Mechanofusion method). Wherein the LATP solid electrolyte material has a weight percentage with respect to the Ni 0.25Mn0.75 O nickel manganese compound material, the weight percentage ranging between 0.2wt.% and 1.0 wt.%. Wherein mechanically mixing the nickel manganese compound material and the solid electrolyte in step S02' comprises mixing at 700rpm for 5 minutes, at 1400rpm for 5 minutes, at 2100rpm for 5 minutes, at 2800rpm for 10 minutes, and at 3500rpm for 10 minutes. The working temperature of mechanically mixing nickel manganese compound material and solid electrolyte is between 25 ℃ and 45 ℃. After the mechanical mixing, a first heat treatment process is performed, as shown in step S03'. Wherein the temperature of the first heat treatment program is in the range of 300 ℃ to 750 ℃, the treatment time of the first heat treatment program is 5 hours to 7 hours, and the heating rate of the first heat treatment program is 2.5 ℃/min.
Thereafter, as shown in step S04', a lithium source, such as lithium hydroxide, is provided, and the lithium source and the aforementioned composite material are mixed and sintered to form a composite positive electrode material. The Ni 0.25Mn0.75 O nickel manganese compound material in the composite material has a mole ratio of 1:1.02 relative to the lithium source. Wherein the sintering in step S04' is a second heat treatment process, the temperature of the second heat treatment process ranges from 300 ℃ to 710 ℃, the treatment time of the second heat treatment process ranges from 24 hours to 30 hours, and the heating rate of the second heat treatment process is 2.5 ℃/min. The composite positive electrode material 1, as shown in fig. 1, comprises a core layer 10 and a coating layer 20, wherein the core layer 10 is made of LiNi 0.5Mn1.5O4, the coating layer 20 coats the core layer 10, and the coating layer 20 is made of LATP solid electrolyte material.
It is noted that in this embodiment, to obtain the best coating effect of the solid electrolyte, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75 O nickel manganese compound material is more controlled between 0.2wt.% and 1.0 wt.%.
Fig. 11A to 11D are SEM images of a composite positive electrode material according to a fourth exemplary embodiment of the present invention. In a fourth example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75 O nickel manganese compound material is 0.2wt.%, and the composite cathode material is prepared by the steps S01 'to S04'.
Fig. 12A to 12D are SEM images of a composite cathode material according to a fifth exemplary embodiment of the present invention. In a fifth example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75 O nickel manganese compound material is 0.3wt.%, and the composite cathode material is prepared by the steps S01 'to S04'.
Fig. 13A to 13D are SEM images of a composite cathode material according to a sixth exemplary embodiment of the present invention. In the sixth example, the weight percentage of the LATP solid electrolyte material relative to the Ni 0.25Mn0.75 O nickel manganese compound material is 0.5wt.%, and the composite cathode material is prepared by the steps S01 'to S04'.
Fig. 14 is a graph showing charge and discharge of potential-capacitance values of a first comparative example, a fourth example, a fifth example, and a sixth example according to the present invention. The button cells manufactured in the first comparative example, the fourth example, the fifth example and the sixth example of the present invention were tested at a charge-discharge rate (C-rate) of 0.1C. The positive electrode plate of button cell is made of positive electrode material, conductive agent and adhesive in the ratio of 94:4:2, and the negative electrode plate is lithium metal. The electrolyte of the button cell included 1.15M lithium hexafluorophosphate (LiPF 6), ethylene carbonate (Ethylene carbonate, EC), diethyl carbonate (Diethyl carbonate, DEC), ethylmethyl carbonate (ETHYL METHYL Carbonate, EMC) and 5wt% fluoroethylene carbonate (Fluoroethylene carbonate, FEC). Wherein the charge-discharge capacitance results of the first and second turns at 0.1C are shown in Table II. In addition, table two further shows the rate performance results of the first comparative example, the fourth example, the fifth example, and the sixth example of the present invention, which were 0.2 charge and then 1C/2C/3C/5C discharge. As shown in fig. 14 and table two, the fourth, fifth and sixth examples of the present invention all had better capacitance performance and rate performance than those of the first comparative example. Therefore, the invention utilizes a dry mechanical mixing method to mix Ni 0.25Mn0.75 O nickel manganese compound material and LATP solid electrolyte material, then adds a lithium source to mix and sinter, thus forming the composite anode material with a core layer and a coating layer, and being capable of helping to improve the capacitance performance and the multiplying power performance of the lithium nickel manganese oxide anode material LMNO.
Watch II
Fig. 15 is a graph showing a cycle life of 1C at room temperature for the first comparative example, the fourth example, the fifth example, and the sixth example of the present invention. The button cells manufactured in the first comparative example, the fourth example, the fifth example and the sixth example of the present invention were tested at a 1C charge-discharge rate (C-rate). As shown in fig. 9, the capacitance storage ratios of the fourth to sixth exemplary embodiments of the present invention are all superior to those of the first comparative example. Therefore, the composite positive electrode material formed by the preparation method can help to improve the cycle performance of the lithium nickel manganese oxide positive electrode material LMNO and prolong the cycle life.
From the above, the present invention controls the weight percentage of the LATP solid electrolyte material to the nickel-manganese compound material such as Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O to be between 0.2wt.% and 1.0wt.%, thereby obtaining a composite positive electrode material with better coating effect. Wherein the weight percentage of LATP solid electrolyte material relative to Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O and other nickel-manganese compound material is preferably in the range of 0.2wt.% to 0.3 wt.%. In other words, the invention can form the coating layer for improving the multiplying power performance of the lithium nickel manganese oxide anode material LMNO by only adding a small amount of lithium aluminum titanium phosphate LATP solid electrolyte, further reduces the manufacturing cost and obtains the optimized coating effect of the solid electrolyte. On the other hand, it is worth noting that the composite positive electrode material of the present invention mixes Lithium Aluminum Titanium Phosphate (LATP) into the pretreatment material of lithium nickel manganese oxide positive electrode material LMNO to synthesize lithium nickel manganese oxide positive electrode material LMNO. The pretreatment material may be, for example, a nickel manganese compound material of Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O, but the coating process is not directly performed using the lithium nickel manganese oxide positive electrode material LMNO.
In a second comparative example, 0.2wt.% of LATP solid electrolyte material was added to a lithium nickel manganese oxide cathode material LMNO having an average particle size of about 15.13 microns and a surface area of 0.31m 2/g. And coating the LATP solid electrolyte material on the surface of the lithium nickel manganese oxide anode material LMNO in the same mixing mode to obtain a second comparative example.
In a third comparative example, 0.2wt.% of LATP solid electrolyte material was added to a lithium nickel manganese oxide cathode material LMNO having an average particle size of about 15.13 microns and a surface area of 0.31m 2/g. And coating the LATP solid electrolyte material on the surface of the lithium nickel manganese oxide anode material LMNO in the same mixing mode, and further sintering to obtain the third comparative example.
Fig. 16 is a graph showing charge and discharge curves of potential-capacitance values of the second and third comparative examples and the first and fourth examples of the present invention. The button cells respectively manufactured in the second comparative example, the third comparative example, the first example and the fourth example of the present invention were tested at a charge-discharge rate (C-rate) of 0.1C. The charge and discharge capacity results of the first and second circles at 0.1C are shown in table three. In addition, table III further shows the results of the rate performance of the samples of the second comparative example, the third comparative example, the first example and the fourth example of the present invention, which were charged at 0.2 and then discharged at 1C/2C/3C/5C. As shown in fig. 16 and table three, the capacitance performance and the rate performance of the first and fourth examples of the present invention are superior to those of the second and third comparative examples. Therefore, the composite positive electrode material prepared by mixing the nickel-manganese compound material and the LATP solid electrolyte material by using the dry mechanical mixing method, adding a lithium source, mixing and sintering is better than the capacitance performance and the multiplying power performance obtained by directly coating the lithium nickel manganese oxide positive electrode material LMNO with the LATP solid electrolyte material.
Watch III
FIG. 17 is a graph showing the cycle life of the third comparative example and the first and fourth examples of the present invention at room temperature 1C. The button cell manufactured by the third comparative example, the first example and the fourth example of the present invention were tested at a 1C charge-discharge rate (C-rate). As shown in fig. 17, the capacitance storage ratios of the first and fourth examples of the present invention are both better than those of the third comparative example, and the cycle life after 200 cycles is about 10% higher than that of the third comparative example. Therefore, the invention can reduce the generation of Mn 3+ by mixing Lithium Aluminum Titanium Phosphate (LATP) into the pretreatment material of the lithium nickel manganese oxide anode material LMNO in a mechanical mode such as a mechanical fusion method (Mechanofusion method) and synthesizing the lithium nickel manganese oxide anode material LMNO, thereby avoiding the dissolution of Mn 3+ in the anode material, the reduction and the deposition of Mn 3+ in the cathode and causing the deterioration of the cycle electrical property.
It should be noted that the invention utilizes the mixing mode of the dry mechanical fusion method (Mechanofusion method) to treat the nickel-manganese compound material and the solid electrolyte, and synchronously completes the surface coating of the solid electrolyte when the lithium manganate positive electrode material LMNO is thermally treated, the process is simple and quick, the obtained composite positive electrode material can truly and effectively improve the performance of the positive electrode material, and is superior to the direct use of the lithium manganate positive electrode material LMNO to coat the solid electrolyte. In addition, in order to obtain the optimized coating effect of the solid electrolyte, the invention can form a coating layer for improving the multiplying power performance of the lithium nickel manganese oxide anode material LMNO by only adding a small amount of lithium titanium aluminum phosphate LATP solid electrolyte, thereby further reducing the manufacturing cost. The method further controls the mode, the working temperature, the rotating speed and the time of mixing the Lithium Aluminum Titanium Phosphate (LATP) and the pretreatment material, prevents the structural defect of the solid electrolyte coating layer caused by the high temperature and excessive friction among particles, and ensures that the lithium nickel manganese oxide anode material LMNO can exert low impedance and good charge and discharge performance through the coating layer of the LATP solid electrolyte. Of course, the composition of the nickel manganese compound material of Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O, the lithium aluminum titanium phosphate (Li 1.3Al0.3Ti1.7(PO4)3, LATP) solid electrolyte, and the lithium nickel manganese oxide positive electrode material (LiNi 0.5Mn1.5O4, LMNO) can be modulated according to practical application requirements. For example, ni xMny(OH)2 or Ni xMny O nickel manganese compound material is mixed with Li 1+zAlzTi2-z(PO4)3 solid electrolyte, x+y=1, z is less than or equal to 2, then lithium source is added, mixed and sintered to form the composite positive electrode material of lithium aluminum titanium phosphate (Li 1+zAlzTi2-z(PO4)3) coated on the surface of lithium nickel manganese oxide positive electrode material LiNi 2xMn2yO4. And will not be described in detail herein.
In summary, the present invention provides a method for preparing a composite positive electrode material, which uses a mixing method of dry mechanical fusion (Mechanofusion method) to process a precursor and a solid electrolyte, so that the surface coating of the solid electrolyte is completed synchronously when the positive electrode material is formed, the process is simple and rapid, and the performance of the positive electrode material can be effectively improved. Aiming at the application of the lithium nickel manganese oxide anode material LMNO coated lithium aluminum titanium phosphate (Li 1.3Al0.3Ti1.7(PO4)3, LATP) solid electrolyte, the invention utilizes a dry mechanical mixing method to mix the nickel manganese compound material of Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O with the solid electrolyte material first, then adding lithium source, mixing and sintering to form the composite anode material with core layer and coating layer. The inner core layer is composed of LiNi 0.5Mn1.5O4 and the outer cladding layer is composed of a solid electrolyte material. Because the Lithium Aluminum Titanium Phosphate (LATP) solid electrolyte has good ion conductivity, when the Lithium Aluminum Titanium Phosphate (LATP) is coated on the surface of the lithium nickel manganese oxide anode material LMNO to form a composite anode material, the lithium nickel manganese oxide anode material LMNO can help to improve the multiplying power performance and the cycle performance of the lithium nickel manganese oxide anode material LMNO, and the Lithium Aluminum Titanium Phosphate (LATP) coating layer can also provide a protective effect to slow down the influence of the damage of the material surface by electrolyte. Furthermore, to obtain an optimal coating effect of the solid electrolyte, the weight percentage of the solid electrolyte material relative to the nickel-manganese compound material such as Ni 0.25Mn0.75(OH)2 or Ni 0.25Mn0.75 O is more preferably controlled between 0.2wt.% and 1.0wt.%, and more preferably between 0.2wt.% and 0.3 wt.%. The invention can form the coating layer for improving the multiplying power performance of the lithium nickel manganese oxide anode material LMNO only by adding a small amount of lithium aluminum titanium phosphate LATP solid electrolyte, and further reduces the manufacturing cost. Compared with the method of directly coating lithium nickel manganese oxide anode material LMNO with Lithium Aluminum Titanium Phosphate (LATP), the method of the invention reduces the generation of Mn 3+ by mixing Lithium Aluminum Titanium Phosphate (LATP) into the pretreatment material of lithium nickel manganese oxide anode material LMNO in a mechanical way such as mechanical fusion method (Mechanofusion method) and synthesizing the lithium nickel manganese oxide anode material LMNO, avoids Mn 3+ from dissolving out in the anode material and reducing in the cathode, deposition causes cyclical electrical degradation. The working temperature of the mixing process is, for example, between 25 ℃ and 45 ℃ and the processing is carried out stepwise for 5 minutes to 30 minutes at a rotational speed in the range 700rpm to 3500 rpm. By controlling the mode, working temperature, rotation speed and time of mixing Lithium Aluminum Titanium Phosphate (LATP) with the pretreatment material, the structural defect of the solid electrolyte coating layer caused by high temperature and excessive friction among particles can be prevented, and meanwhile, the lithium nickel manganese oxide anode material LMNO can exert low impedance and good charge and discharge performance through the coating layer of the LATP solid electrolyte.
The present invention is susceptible to various modifications by those skilled in the art without departing from the scope of the invention as defined in the appended claims.
Symbol description:
1: composite positive electrode material
10: Core layer
11: Li+ ion
20: Coating layer
30: Electrolyte composition
S01-S04, S00 '-S04': step (a)

Claims (13)

1.一种复合式正极材料的制备方法，包括步骤：1. A method for preparing a composite positive electrode material, comprising the steps of: (a)提供一镍锰化合物材料，其中该镍锰化合材料为NixMny(OH)2或NixMnyO，x+y＝1；(a) providing a nickel-manganese compound material, wherein the nickel-manganese compound material is Ni x Mn y (OH) 2 or Ni x Mn y O, x + y = 1; (b)提供一固态电解质材料，并将该镍锰化合物材料以及该固态电解质材料以一机械方式混合成一复合材料，其中该固态电解质材料相对该镍锰化合物材料具有一重量百分比，该重量百分比的范围介于0.2wt.％至1.0wt.％之间；以及(b) providing a solid electrolyte material, and mechanically mixing the nickel-manganese compound material and the solid electrolyte material into a composite material, wherein the solid electrolyte material has a weight percentage relative to the nickel-manganese compound material, and the weight percentage ranges from 0.2wt.% to 1.0wt.%; and (c)提供一锂源，混合该锂源以及该复合材料，并烧结形成该复合式正极材料，其中该复合式正极材料包括一核心层以及一包覆层，且该核心层由LiNi2xMn2yO4所构成，其中该包覆层包覆该核心层，该包覆层由该固态电解质材料所构成。(c) providing a lithium source, mixing the lithium source and the composite material, and sintering to form the composite positive electrode material, wherein the composite positive electrode material comprises a core layer and a coating layer, and the core layer is composed of LiNi 2x Mn 2y O 4 , wherein the coating layer covers the core layer, and the coating layer is composed of the solid electrolyte material. 2.如权利要求1所述的正极材料的制备方法，其中该镍锰化合物材料为Ni0.25Mn0.75(OH)2，该步骤(b)于该机械方式混合后包括一第一热处理程序，该第一热处理温度范围介于300℃至850℃，该第一热处理程序的处理时间5小时至7小时，该第一热处理程序的升温速率2.5℃/分钟。2. The method for preparing a positive electrode material as claimed in claim 1, wherein the nickel-manganese compound material is Ni 0.25 Mn 0.75 (OH) 2 , and the step (b) comprises a first heat treatment process after the mechanical mixing, the first heat treatment temperature ranges from 300° C. to 850° C., the treatment time of the first heat treatment process is 5 hours to 7 hours, and the heating rate of the first heat treatment process is 2.5° C./minute. 3.如权利要求1所述的正极材料的制备方法，其中该镍锰化合物材料为Ni0.25Mn0.75O，该步骤(a)包括一预氧化程序，该预氧化程序的温度范围介于300℃至850℃，该预氧化程序的处理时间5小时至7小时，该预氧化程序的升温速率2.5℃/分钟。3. The method for preparing a positive electrode material as claimed in claim 1, wherein the nickel-manganese compound material is Ni 0.25 Mn 0.75 O, and the step (a) includes a pre-oxidation process, the temperature range of the pre-oxidation process is between 300° C. and 850° C., the processing time of the pre-oxidation process is 5 hours to 7 hours, and the heating rate of the pre-oxidation process is 2.5° C./minute. 4.如权利要求3所述的正极材料的制备方法，其中该步骤(b)于该机械方式混合后更包括一第一热处理程序，该第一热处理程序的温度范围介于300℃至750℃，该第一热处理程序的处理时间5小时至7小时，该第一热处理程序的升温速率2.5℃/分钟。4. The method for preparing a positive electrode material as described in claim 3, wherein the step (b) further includes a first heat treatment process after the mechanical mixing, the temperature range of the first heat treatment process is between 300°C and 750°C, the treatment time of the first heat treatment process is 5 hours to 7 hours, and the heating rate of the first heat treatment process is 2.5°C/minute. 5.如权利要求1所述的正极材料的制备方法，其中该步骤(b)中该机械方式混合该镍锰化合物材料以及该固态电解质包含以700rpm转速混合5分钟，以1400rpm转速混合5分钟，以2100rpm转速混合5分钟，以2800rpm转速混合10分钟，并以3500rpm转速混合10分钟。5. The method for preparing a positive electrode material as claimed in claim 1, wherein the mechanical mixing of the nickel-manganese compound material and the solid electrolyte in step (b) comprises mixing at 700 rpm for 5 minutes, mixing at 1400 rpm for 5 minutes, mixing at 2100 rpm for 5 minutes, mixing at 2800 rpm for 10 minutes, and mixing at 3500 rpm for 10 minutes. 6.如权利要求1所述的正极材料的制备方法，其中该步骤(b)中该机械方式混合该镍锰化合物材料以及该固态电解质之工作温度介于25℃至45℃之间。6. The method for preparing the positive electrode material as claimed in claim 1, wherein the working temperature of the mechanical mixing of the nickel-manganese compound material and the solid electrolyte in the step (b) is between 25°C and 45°C. 7.如权利要求1所述的正极材料的制备方法，其中该固态电解质之化学式为Li1+ zAlzTi2-z(PO4)3，z≦2。7 . The method for preparing a positive electrode material as claimed in claim 1 , wherein the chemical formula of the solid electrolyte is Li 1+ z Al z Ti 2-z (PO 4 ) 3 , z≦2. 8.如权利要求1所述的正极材料的制备方法，其中该机械方式包括一机械融合法。8. The method for preparing the positive electrode material as claimed in claim 1, wherein the mechanical method comprises a mechanical fusion method. 9.如权利要求1所述的正极材料的制备方法，其中该步骤(c)中系以一机械方式混合该锂源以及该复合材料，包含以700rpm转速混合5分钟，并以1400rpm转速混合30分钟。9. The method for preparing a positive electrode material as claimed in claim 1, wherein in step (c), the lithium source and the composite material are mixed mechanically, comprising mixing at a rotation speed of 700 rpm for 5 minutes and mixing at a rotation speed of 1400 rpm for 30 minutes. 10.如权利要求1所述的正极材料的制备方法，其中该步骤(c)包括一第二热处理程序，该第二热处理程序的温度范围介于300℃至710℃，该第二热处理程序的处理时间24小时至30小时，该第二热处理程序的升温速率2.5℃/分钟。10. The method for preparing a positive electrode material as described in claim 1, wherein the step (c) includes a second heat treatment process, the temperature range of the second heat treatment process is between 300°C and 710°C, the treatment time of the second heat treatment process is 24 hours to 30 hours, and the heating rate of the second heat treatment process is 2.5°C/minute. 11.如权利要求1所述的正极材料的制备方法，其中该步骤(c)中该复合材料中的该镍锰化合物材料相对该锂源具有一莫耳数比1:1.02。11. The method for preparing a positive electrode material as claimed in claim 1, wherein in the step (c), the nickel-manganese compound material in the composite material has a molar ratio of 1:1.02 to the lithium source. 12.如权利要求1所述的正极材料的制备方法，其中该重量百分比的范围介于0.2wt.％至0.3wt.％之间。12 . The method for preparing the positive electrode material as claimed in claim 1 , wherein the weight percentage ranges from 0.2 wt. % to 0.3 wt. %. 13.如权利要求1所述的正极材料的制备方法，其中该镍锰化合材料的平均粒径范围介于10微米至20微米之间，该固态电解质材料的平均粒径范围介于1微米至5微米之间。13. The method for preparing a positive electrode material as claimed in claim 1, wherein the average particle size of the nickel-manganese compound material is between 10 microns and 20 microns, and the average particle size of the solid electrolyte material is between 1 micron and 5 microns.
CN202310495188.0A 2023-05-05 2023-05-05 Preparation method of composite positive electrode material Withdrawn CN118899408A (en)

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Application publication date: 20241105