CN114388797A - Coated lithium ion battery ternary cathode material and preparation method and application thereof - Google Patents
Coated lithium ion battery ternary cathode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114388797A CN114388797A CN202111554723.2A CN202111554723A CN114388797A CN 114388797 A CN114388797 A CN 114388797A CN 202111554723 A CN202111554723 A CN 202111554723A CN 114388797 A CN114388797 A CN 114388797A
- Authority
- CN
- China
- Prior art keywords
- source
- ion battery
- lithium ion
- cobalt
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M10/05—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
- H01M4/13—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a coated lithium ion battery ternary cathode material and a preparation method and application thereof, wherein the coated lithium ion battery ternary cathode material comprises a base material, wherein the base material is nickel cobalt lithium manganate; and a coating layer formed on the surface of the base material, wherein the coating layer is Ca3Al2(GeO4)3. The coated ternary cathode material for the lithium ion battery has excellent performance, and can not only realize high-efficiency ion transmissionAnd the ternary cathode material has less contact reaction, so that the ion exchange between the ternary cathode material and electrolyte is not influenced, the cycle performance of the ternary cathode material is favorably improved, and the discharge platform and the rate discharge capacity of the material under the rate are obviously improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a coated lithium ion battery ternary anode material and a preparation method thereof, and also relates to application of the coated lithium ion battery ternary anode material as an anode active substance in a lithium ion battery anode plate and a lithium ion battery.
Background
The nickel-cobalt-manganese ternary battery material, also called as an NCM ternary material, is different from the traditional lithium ion battery anode materials of Lithium Cobaltate (LCO) and lithium iron phosphate (LFP), and the layered ternary nickel-cobalt-manganese (NCM) anode material has higher specific capacity and safety.
However, with increasing proportion of Ni ions as the main capacity contribution, NCM materials will also face higher risks of safety and capacity fade. The current common approaches to this problem are: the main solution is to coat a layer of stable nano material on the surface of the NCM anode material to reduce the direct contact between the electrolyte and the anode material and prevent the side reaction, and the most used coating agents at present are metal oxides, phosphates and fluorides.
The existing coating means of metal oxide and the like mainly forms a core-shell-like structure by taking NCM as a center and taking a compact coating as a shell and partially non-compact modifier modification, the formed coating is not uniform, the non-uniform coating leaves more defects on the surface of the material, and the contact and reaction between electrolyte and the material cannot be completely prevented.
Disclosure of Invention
In view of the above, the present invention is directed to a coated ternary positive electrode material for lithium ion battery, which comprises a NCM ternary material as a base material and Ca formed on the surface of the NCM ternary material3Al2(GeO4)3The formed coating layer can obtain a more stable and better-performance coated lithium ion battery ternary cathode material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a coated ternary anode material of a lithium ion battery, which comprises the following components:
the base material is nickel cobalt lithium manganate;
and a coating layer formed on the surface of the base material, wherein the coating layer is Ca3Al2(GeO4)3。
The invention further provides a preparation method of the coated lithium ion battery ternary cathode material, which comprises the following steps:
obtaining a coating precursor, wherein the coating precursor is obtained by uniformly mixing a calcium source, an aluminum source and a germanium source with the molar ratio of Ca, Al and Ge elements being 3:2:3, drying and presintering;
stirring and dispersing a lithium source, a nickel source, a cobalt source and a manganese source in a solvent, and regulating and controlling the pH value to 7.2-7.4 to obtain a mixed solution;
mixing and dispersing the coating precursor and the mixed solution, and then freeze-drying and calcining to prepare Ca3Al2(GeO4)3The nickel-cobalt-manganese ternary cathode material is coated.
Further, the calcium source is at least one selected from calcium oxide, calcium hydroxide, calcium carbonate and calcium bicarbonate;
the aluminum source is selected from at least one of aluminum oxide, aluminum hydroxide and aluminum peroxide;
the germanium source is at least one of germanium dioxide and germanium monoxide.
In the step of obtaining the coated precursor, the uniform mixing is performed in a ball milling dispersion mode, wherein the ball milling rotation speed is 400-;
the drying temperature is 82-85 ℃, and the drying time is 10-15 h;
the pre-sintering process comprises the following steps: sintering for 4-8h at the temperature of 450-600 ℃ in the air atmosphere.
Further, the lithium source is at least one selected from lithium carbonate and lithium hydroxide;
the nickel source is selected from at least one of nickel sulfate, nickel nitrate and nickel chloride;
the cobalt source is selected from at least one of cobalt sulfate, cobalt nitrate and cobalt chloride;
the manganese source is selected from at least one of manganese sulfate, manganese nitrate and manganese chloride.
Further, in the step of obtaining the mixed solution, the solvent is selected from a hydroxyethyl cellulose solution, a carboxymethyl cellulose solution, a polyvinyl alcohol solution, a polyacrylic acid solution or a polyethylene glycol solution; the stirring speed of the stirring dispersion is 200-300rpm, and the time is 2-4 h.
In a further scheme, the temperature of the freeze drying is-60 to-15 ℃, and the pressure is 0.05 to 1.0 MPa.
In a further scheme, the calcining process specifically comprises the following steps: under the air atmosphere, heating to 900-1000 ℃ at the speed of 2-3 ℃/min, and preserving heat for 4-10 h; then the temperature is reduced at the speed of 4-8 ℃/min.
The invention further provides a lithium ion battery positive plate which comprises a positive active material, wherein the positive active material is any one of the coating type lithium ion battery ternary positive electrode materials.
The invention further provides a lithium ion battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode adopts the positive plate.
Compared with the prior art, the invention has the following beneficial effects:
ca to be porous according to the present invention3Al2(GeO4)3The uniform coating is formed on the surface of the nickel-cobalt-manganese ternary cathode material due to Ca3Al2(GeO4)3The stability and structure of the material make the material show more excellent performance after coating, not only can high-efficiency ion transmission be realized, but also fewer contact reactions are realized, so that the ion exchange between the ternary cathode material and the electrolyte is not influenced, and the performance of the ternary cathode material is improved.
The invention controls Ca3Al2(GeO4)3The coating amount not only avoids the direct contact of the ternary anode material and the electrolyte, but also does not influence the extraction of lithium ions, prevents the surface reaction of the electrode material, improves the surface stability of the electrode material, and prolongs the cycle number of the battery.
Further, Ca3Al2(GeO4)3The nickel-cobalt-manganese ternary cathode material is uniformly coated on the surface of the nickel-cobalt-manganese ternary cathode material, so that the nickel-cobalt-manganese ternary cathode material is acted by the coating force, the deformation of the ternary cathode material due to the action of releasing and embedding lithium ions in the reaction process of the battery can be reduced, the coating is more uniform and more stable, the structural stability of the ternary cathode material is better, the cycle performance of the battery is higher,the invention can improve the rate discharge performance of the material, and can obviously improve the discharge platform and rate discharge capacity of the material under the rate.
Drawings
FIG. 1 is an XRD of the ternary cathode material of the coated lithium ion battery prepared in example 1;
fig. 2-3 are scanning electron micrographs of the coated lithium ion battery ternary cathode material prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a coated lithium ion battery ternary cathode material in a first aspect, which comprises the following components:
the base material is nickel cobalt lithium manganate;
and a coating layer formed on the surface of the base material, wherein the coating layer is Ca3Al2(GeO4)3。
The invention takes a nickel-cobalt-manganese ternary material as a base material, wherein the nickel-cobalt-manganese lithium manganate is a material well known by technical personnel in the field and has a chemical general formula of LiNixCoyMn1-x-yO2Wherein x is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.9, and x + y is less than 1, the specific stoichiometric ratio can be selected according to the actual situation, and different ternary materials, such as NCM523, NCM622, NCM811 and the like can be obtained by selecting different stoichiometric ratios of nickel, cobalt and manganese, and are not specifically described herein. Forming a coating layer Ca on the surface3Al2(GeO4)3The coating layer uniformly covers the surface of the base material, so that a certain coating force is generated on the base material, the deformation of the ternary material due to the action of lithium ions released and inserted in the reaction process of the battery is reduced, the coating is more uniform and more stable, the structural stability of the ternary anode material is better, and the cycle performance of the battery is higher.
Due to Ca3Al2(GeO4)3The coating is uniform due to the stable characteristic and the structural characteristic of the lithium ion battery, so that the direct contact between the ternary anode material and the electrolyte is avoided, the desorption of lithium ions is not influenced, the surface reaction of the electrode material is prevented, the surface stability of the electrode material is improved, and the cycle number of the battery is prolonged. And due to Ca3Al2(GeO4)3The coating layer is in a porous structure, so that ion exchange between the ternary cathode material and electrolyte is not influenced, and the performance of the ternary cathode material is improved.
The invention provides a preparation method of a coated lithium ion battery ternary cathode material, which mainly comprises the following steps:
obtaining a coated precursor
Specifically, the calcium source, the aluminum source and the germanium source with the molar ratio of Ca, Al and Ge elements of 3:2:3 are uniformly mixed, dried and pre-sintered to obtain the calcium-germanium-based catalyst. According to the embodiment of the present invention, the obtainment of the calcium source, the aluminum source and the germanium source is not particularly limited, and specifically, there may be mentioned as an example that the calcium source may be at least one of calcium oxide, calcium hydroxide, calcium carbonate, calcium hydrogen carbonate; the aluminum source can be at least one of aluminum oxide, aluminum hydroxide and aluminum peroxide; the germanium source may be at least one of germanium dioxide and germanium monoxide. The calcium source, the aluminum source and the germanium source can be uniformly mixed by ball milling and dispersing, the specific parameters can be adjusted according to needs and actual conditions as long as the purpose of uniform dispersion can be realized, in one or more embodiments of the invention, the ball milling rotation speed is 400-500rpm, and the time is 6-8 h. Drying, pre-sintering and the like are all conventional parameter adjustment in the field, and in some embodiments of the invention, the drying temperature is 82-85 ℃ and the drying time is 10-15 h; the pre-sintering process comprises the following steps: sintering at the temperature of 450-600 ℃ for 4-8h in the air atmosphere, wherein the heating rate is preferably 1 ℃/min.
Providing a nickel-cobalt-manganese ternary material mixed solution
The mixed solution can be obtained by adopting the conventional means in the field, specifically, a lithium source, a nickel source, a cobalt source and a manganese source are stirred and dispersed in a solvent according to the stoichiometric ratio of the nickel cobalt lithium manganate, and the pH is regulated to be 7.2-7.4, so as to obtain the mixed solution, wherein the molar ratio of the sum of the lithium source and the nickel cobalt manganese is (1.01-1.05): 1, which is a conventional composition in the art, and is not specifically described herein. The lithium source, the nickel source, the cobalt source and the manganese source are all conventional choices in the field, and specific examples that can be mentioned are that the lithium source can be at least one of lithium carbonate and lithium hydroxide; the nickel source can be at least one of nickel sulfate, nickel nitrate and nickel chloride; the cobalt source can be at least one of cobalt sulfate, cobalt nitrate and cobalt chloride; the manganese source may be at least one of manganese sulfate, manganese nitrate, manganese chloride. The dispersing solvent can be selected from hydroxyethyl cellulose solution, carboxymethyl cellulose solution, polyvinyl alcohol solution, polyacrylic acid solution or polyethylene glycol solution; the stirring speed for stirring and dispersing is 200-300rpm, and the time is 2-4 h.
3 2 4 3The CaAl (GeO) -coated nickel-cobalt-manganese ternary positive electrode material is prepared
And mixing and dispersing the coating precursor and the mixed solution, and then freeze-drying and calcining to obtain the coating precursor. In embodiments according to the present invention, the thickness of the coating layer can be adjusted by adjusting the amount of the coating precursor, and in particular embodiments of the present invention, the amount of the precursor added is 1.5 to 3.2% of the total mass of the lithium source, the nickel source, the cobalt source, and the manganese source. The temperature of the freeze drying is-60 to-15 ℃, and the pressure is 0.05 to 1.0 MPa; the calcining process specifically comprises the following steps: heating to 900-class 1000 ℃ at the heating rate of 2-3 ℃/min under the air atmosphere, and preserving heat for 4-10 h; then the temperature is reduced by controlling the temperature reduction rate at 4-8 ℃/min.
The invention further provides a lithium ion battery positive plate which comprises a positive active material, wherein the positive active material is the coated lithium ion battery ternary positive material in the first aspect of the invention or the coated lithium ion battery ternary positive material prepared by the preparation method in the second aspect of the invention. It is understood that other auxiliary agents conventionally used in the art, such as conductive agents, etc., are also included and will not be specifically described herein. The positive plate has the same advantages and effects as the positive plate.
The invention further provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode adopts the positive plate in the third aspect of the invention.
The present invention is illustrated below by way of specific examples, which are intended to be illustrative only and not to limit the scope of the present invention in any way, and reagents and materials used therein are commercially available, unless otherwise specified, and conditions or steps thereof are not specifically described.
Example 1
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide and germanium dioxide in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, carrying out ball milling dispersion for 8h at 400rpm, placing the ball-milled mixture in an oven at 82 ℃ for drying for 15h, heating the dried mixture to 450 ℃ at the heating rate of 1 ℃/min under the air condition in a muffle furnace, keeping the temperature for 8h under the condition, and naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at a rotating speed of 200r/min for 4 hours, slowly dropwise adding an ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH of the mixed solution to 7.4 to obtain a mixed solution;
adding the precursor into the mixed solution, wherein the content of the precursor A accounts for 1.5 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion at 400rpm for 8 hours, and performing freeze drying on the ball-milled mixture in a freeze dryer at-15 ℃ and 0.05 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 1000 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 4h under the condition, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 8 ℃/min, and cooling to room temperature to obtain the product with the surface coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Fig. 1 is an XRD spectrum of the coated lithium ion battery ternary cathode material prepared in this example, and it can be seen that the characteristic peak is nickel-cobalt-manganese and has no impurity peak, and the peak of the coating layer is very weak.
Fig. 2 to 3 are scanning electron microscope images of the coated lithium ion battery ternary cathode material prepared in this embodiment, and it can be seen from the images that the coated lithium ion battery ternary cathode material has an obvious particle structure, and the coating layer and the particle layer are tightly coated.
Example 2
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, and performing ball milling dispersion under the condition of 450rpm for 7 hours. The ball-milled mixture was dried in an oven at 83 ℃ for 12 h. The dried mixture was heated to 500 ℃ in a muffle furnace under air at a heating rate of 1 ℃/min and held for 6h under these conditions. Naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at a rotating speed of 250r/min for 3 hours, slowly dropwise adding an ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH of the mixed solution to 7.3 to obtain a mixed solution;
adding a precursor into the mixed solution, wherein the content of the precursor accounts for 1.5 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion for 6 hours at 450rpm, and performing freeze drying on the ball-milled mixture in a freeze dryer at-30 ℃ and 0.50 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 950 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 7h, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 6 ℃/min, and cooling to room temperature to obtain the product with the surface coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Example 3
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, and performing ball milling dispersion for 6 hours under the condition of 500 rpm. And drying the ball-milled mixture in an oven at 85 ℃ for 10 h. The dried mixture was heated to 600 ℃ in a muffle furnace under air conditions at a heating rate of 1 ℃/min and held under these conditions for 4 h. Naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2 hours, slowly dripping ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH value of the mixed solution to 7.4 to obtain a mixed solution;
adding a precursor into the mixed solution, wherein the content of the precursor accounts for 2.0 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion for 4 hours at 500rpm, and performing freeze drying on the ball-milled mixture in a freeze dryer at-45 ℃ and 0.75 MPa;
placing the freeze-dried mixture in a muffle furnace under air atmosphere toHeating to 900 deg.C at a rate of 2 deg.C/min, maintaining for 10 hr, naturally cooling to 4 deg.C/min, and cooling to room temperature to obtain a product coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Example 4
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, and performing ball milling dispersion under the condition of 400rpm for 8 hours. And drying the ball-milled mixture in an oven at 85 ℃ for 10 h. The dried mixture was heated to 600 ℃ in a muffle furnace under air conditions at a heating rate of 1 ℃/min and held under these conditions for 4 h. Naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at a rotating speed of 200r/min for 4 hours, slowly dropwise adding an ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH of the mixed solution to 7.2 to obtain a mixed solution;
adding the precursor into the mixed solution, wherein the content of the precursor A accounts for 1.5 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion for 8 hours at 400rpm, and performing freeze drying on the ball-milled mixture in a freeze dryer at-60 ℃ and 1.00 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 900 ℃ at the speed of 3 ℃/min in the air atmosphere, keeping the temperature for 10h, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 4 ℃/min, and cooling to room temperature to obtain the product with the surface coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Example 5
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, and performing ball milling dispersion for 6 hours under the condition of 500 rpm. And drying the ball-milled mixture in an oven at 85 ℃ for 10 h. The dried mixture was heated to 450 ℃ in a muffle furnace under air conditions at a heating rate of 1 ℃/min and held under these conditions for 8 h. Naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2 hours, slowly dripping ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH value of the mixed solution to 7.4 to obtain a mixed solution;
adding the precursor into the mixed solution, wherein the content of the precursor A accounts for 3.2 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion at 400rpm for 8 hours, and performing freeze drying on the ball-milled mixture in a freeze dryer at-30 ℃ and 0.10 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 6h, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 4 ℃/min, and cooling to room temperature to obtain the product with the surface coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Example 6
The preparation method of the ternary cathode material of the coated lithium ion battery comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, and performing ball milling dispersion for 6 hours under the condition of 500 rpm. The ball-milled mixture was dried in an oven at 82 ℃ for 15 h. The dried mixture was heated to 450 ℃ in a muffle furnace under air conditions at a heating rate of 1 ℃/min and held under these conditions for 8 h. Naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2 hours, slowly dripping ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH value of the mixed solution to 7.3 to obtain a mixed solution;
adding a precursor into the mixed solution, wherein the content of the precursor accounts for 3.0 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, performing ball milling in a ball milling tank, performing ball milling dispersion for 4 hours at 500rpm, and performing freeze drying on the ball-milled mixture in a freeze dryer at-60 ℃ and 1.00 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 4h under the condition, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 8 ℃/min, and cooling to room temperature to obtain the product with the surface coated with Ca3Al2(GeO4)3The lithium ion battery ternary positive electrode material NCM 622.
Comparative example 1
The comparative example is an uncoated NCM622 ternary cathode material, and the specific preparation steps are as follows:
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2 hours, slowly dripping ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH value of the mixed solution to 7.4 to obtain a mixed solution;
ball-milling the mixed solution in a ball-milling tank, carrying out ball-milling dispersion for 4h at 500rpm, and freeze-drying the ball-milled mixture in a freeze dryer at-45 ℃ and 0.75 MPa;
and (3) placing the mixture after freeze drying in a muffle furnace, heating to 900 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 10h under the condition, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 4 ℃/min, and cooling to room temperature to obtain the ternary cathode material NCM622 of the lithium ion battery.
Comparative example 2
The preparation method of the ternary cathode material of the coated lithium ion battery in the comparative example comprises the following specific steps:
weighing calcium carbonate, aluminum hydroxide, germanium dioxide and zirconia balls in a ball milling tank according to the molar ratio of Ca, Al and Ge elements of 3:2:3, adding absolute ethyl alcohol, dispersing at 500rpm, and ball milling for 6 hours. And drying the ball-milled mixture in an oven at 85 ℃ for 10 h. Heating the dried mixture to 450 ℃ at the heating rate of 1 ℃/min in a muffle furnace under the air condition, keeping the temperature for 10 hours under the condition, and naturally cooling to obtain a precursor;
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing a certain amount of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in a polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2 hours, slowly dropwise adding an ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH of the mixed solution to 7.4 to obtain a mixed solution;
adding the precursor into the mixed solution to enable the content of the precursor to be 4.0 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, carrying out ball milling in a ball milling tank, carrying out ball milling dispersion for 8 hours at 400rpm, and carrying out freeze drying on the ball-milled mixture in a freeze dryer at-30 ℃ and 0.10 MPa;
placing the mixture after freeze drying in a muffle furnace, heating to 1000 ℃ at the speed of 2 ℃/min in the air atmosphere, keeping the temperature for 6h, naturally cooling after the heat preservation process is finished, keeping the cooling speed at 4 ℃/min, and obtaining the final Ca after the temperature is reduced to room temperature3Al2(GeO4)3Coated NCM 622.
Comparative example 3
The product in this comparative example was coated Al2O3And Nb2O5The modified NCM622 ternary cathode material is prepared by the following specific steps:
according to the weight ratio of Li: ni: co: mn: the element molar ratio is 1.01: 0.6:0.2:0.2, weighing a certain amount of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, dissolving in the polyethylene glycol solution, stirring at the rotating speed of 300r/min for 2h, slowly dripping ammonia-ammonium chloride buffer solution in the stirring process, and adjusting the pH value of the mixed solution to 7.4 to obtain the mixed solution. Freeze-drying in a freeze-drying machine at-30 deg.C under 0.10MPa to obtain a mixture I;
weighing a certain amount of Al2O3And Nb2O5The element Al: nb in a molar ratio of 1:1 and Al2O3And Nb2O5The total mass of the aluminum alloy is 3.2 percent of the total mass of lithium carbonate, nickel sulfate, cobalt oxide and manganese chloride, and Al is weighed in sequence2O3And Nb2O5Adding the mixture and the mixture into a mixing tank, uniformly mixing the mixture and the mixture by using a planetary stirrer, carrying out ball milling in a ball milling tank, and dispersing for 8 hours at 400rpm to obtain a mixture II;
placing the mixture II into a crucible, calcining the mixture II in a muffle furnace under the air atmosphere at the constant temperature of 1000 ℃ for 6 hours, and cooling to room temperature at the cooling rate of 4 ℃/min to obtain a block material;
the block materials are crushed after being discharged from the furnace and are sieved by a 200-mesh sieve to obtain the coated Al2O3And Nb2O5Modified NCM622 ternary positive electrode material.
Test example
The simulated batteries assembled by using the materials prepared in examples 1 to 6 and comparative examples 1 to 3 as the positive electrode materials, the battery-grade lithium sheets as the negative electrode materials and the lithium hexafluorophosphate as the main component as the electrolyte were subjected to the relevant tests, wherein the charge-discharge electrochemical window was 3.0 to 4.3V, and the high-temperature performance test method was 55 ℃/1C rate cycle, and the results are shown in table 1.
Table 1 comparison of test data for examples and comparative examples
Example 3 preparationThe 0.2C rate specific discharge capacity of the modified NCM622 material is 177.89mAh/g, the 1C rate specific discharge capacity is 167.17mAh/g, the capacity retention rate is 99.76% after 50 cycles at 55 ℃; the battery prepared from the unmodified material in the comparative example 1 has the specific discharge capacity of 156.84mAh/g at the rate of 0.2C, the specific discharge capacity of 150.61mAh/g at the rate of 1C, the capacity retention rate of 91.64 percent after 55 ℃ and 50 cycles. Description by Ca3Al2(GeO4)3The coated NCM622 significantly improves the rate capability and the high-temperature cycle performance.
The modified NCM622 material prepared in example 5 has 0.2C rate specific discharge capacity of 177.25mAh/g, 1C rate specific discharge capacity of 164.87mAh/g, 55 ℃, and a capacity retention rate of 99.68% after 50 cycles; the battery made of the material of comparative example 2, in which the coating amount exceeded the specified range, had a specific discharge capacity at 0.2C rate of 171.44mAh/g, a specific discharge capacity at 1C rate of 162.37mAh/g, a capacity retention rate of 94.46% after 55℃ cycles.
Different Metal oxides Al prepared in comparative example 32O3And Nb2O5The 0.2C rate specific discharge capacity of the modified NCM622 ternary cathode material is 162.37mAh/g, the 1C rate specific discharge capacity is 158.79mAh/g, the capacity retention rate is 93.15% after 50 cycles at 55 ℃.
As can be seen from the test results in Table 1, it is demonstrated that Ca is passed in comparison with the test results of comparative examples 1 to 33Al2(GeO4)3The coating can remarkably improve the rate capability and the high-temperature cycle performance of the NCM622, so that the NCM622 has excellent safety performance, and the battery made of the material prepared in the embodiment has more excellent electrochemical performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A coated ternary cathode material for a lithium ion battery is characterized by comprising:
the base material is nickel cobalt lithium manganate;
and a coating layer formed on the surface of the base material, wherein the coating layer is Ca3Al2(GeO4)3。
2. A preparation method of a coated lithium ion battery ternary cathode material is characterized by comprising the following steps:
obtaining a coating precursor, wherein the coating precursor is obtained by uniformly mixing a calcium source, an aluminum source and a germanium source with the molar ratio of Ca, Al and Ge elements being 3:2:3, drying and presintering;
stirring and dispersing a lithium source, a nickel source, a cobalt source and a manganese source in a solvent, and regulating and controlling the pH value to 7.2-7.4 to obtain a mixed solution;
mixing and dispersing the coating precursor and the mixed solution, and then freeze-drying and calcining to prepare Ca3Al2(GeO4)3The nickel-cobalt-manganese ternary cathode material is coated.
3. The method according to claim 2, wherein the calcium source is at least one selected from the group consisting of calcium oxide, calcium hydroxide, calcium carbonate, and calcium bicarbonate;
the aluminum source is selected from at least one of aluminum oxide, aluminum hydroxide and aluminum peroxide;
the germanium source is at least one of germanium dioxide and germanium monoxide.
4. The preparation method according to claim 2, wherein in the step of obtaining the coating precursor, the mixing is performed by ball milling dispersion, wherein the ball milling rotation speed is 400-500rpm and the time is 6-8 h;
the drying temperature is 82-85 ℃, and the drying time is 10-15 h;
the pre-sintering process comprises the following steps: sintering for 4-8h at the temperature of 450-600 ℃ in the air atmosphere.
5. The method according to claim 2, wherein the lithium source is at least one selected from lithium carbonate and lithium hydroxide;
the nickel source is selected from at least one of nickel sulfate, nickel nitrate and nickel chloride;
the cobalt source is selected from at least one of cobalt sulfate, cobalt nitrate and cobalt chloride;
the manganese source is selected from at least one of manganese sulfate, manganese nitrate and manganese chloride.
6. The production method according to claim 2, wherein in the step of obtaining the mixed solution, the solvent is selected from a hydroxyethyl cellulose solution, a carboxymethyl cellulose solution, a polyvinyl alcohol solution, a polyacrylic acid solution, or a polyethylene glycol solution; the stirring speed of the stirring dispersion is 200-300rpm, and the time is 2-4 h.
7. The method of claim 2, wherein the freeze-drying temperature is-60 to-15 ℃ and the pressure is 0.05 to 1.0 MPa.
8. The preparation method according to claim 2, wherein the calcination process comprises: under the air atmosphere, heating to 900-1000 ℃ at the speed of 2-3 ℃/min, and preserving heat for 4-10 h; then the temperature is reduced at the speed of 4-8 ℃/min.
9. The lithium ion battery positive plate comprises a positive active material, and is characterized in that the positive active material is the coated lithium ion battery ternary positive material in the claim 1 or the coated lithium ion battery ternary positive material prepared by the preparation method in any one of the claims 2 to 8.
10. A lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode employs the positive electrode sheet according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111554723.2A CN114388797B (en) | 2021-12-17 | 2021-12-17 | Coated lithium ion battery ternary cathode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111554723.2A CN114388797B (en) | 2021-12-17 | 2021-12-17 | Coated lithium ion battery ternary cathode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114388797A true CN114388797A (en) | 2022-04-22 |
| CN114388797B CN114388797B (en) | 2023-04-11 |
Family
ID=81197177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111554723.2A Active CN114388797B (en) | 2021-12-17 | 2021-12-17 | Coated lithium ion battery ternary cathode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114388797B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364737A (en) * | 2001-01-09 | 2002-08-21 | 中国科学院长春光学精密机械与物理研究所 | Rare earth doped germanate glass and its preparing method |
| CN1780895A (en) * | 2003-04-30 | 2006-05-31 | 纳米技术有限公司 | Core/shell nanoparticles suitable for (f)ret-assays |
| CN104364956A (en) * | 2012-06-20 | 2015-02-18 | 丰田自动车株式会社 | Battery system, method for manufacturing battery system, and battery control apparatus |
| CN104409705A (en) * | 2014-12-20 | 2015-03-11 | 宫香娥 | Preparation method of carbon-coated germanium-doped lithium manganate composite cathode material |
| US20150228971A1 (en) * | 2014-02-07 | 2015-08-13 | Samsung Sdi Co., Ltd. | Positive active material, positive electrode and lithium battery including the positive active material, and method of manufacturing the positive active material |
| JP2018022637A (en) * | 2016-08-05 | 2018-02-08 | Tdk株式会社 | Positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN111987303A (en) * | 2020-08-12 | 2020-11-24 | 中南大学 | Titanium germanium aluminum lithium phosphate modified high-nickel cathode material and preparation method thereof |
| CN112447967A (en) * | 2019-09-02 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, positive electrode plate and lithium ion secondary battery |
| CN113471411A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Composite coated positive electrode material and preparation method thereof |
| CN113471414A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Lithium ion battery composite positive electrode material and preparation method and application thereof |
-
2021
- 2021-12-17 CN CN202111554723.2A patent/CN114388797B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364737A (en) * | 2001-01-09 | 2002-08-21 | 中国科学院长春光学精密机械与物理研究所 | Rare earth doped germanate glass and its preparing method |
| CN1780895A (en) * | 2003-04-30 | 2006-05-31 | 纳米技术有限公司 | Core/shell nanoparticles suitable for (f)ret-assays |
| US20070087195A1 (en) * | 2003-04-30 | 2007-04-19 | Nanosolutions Gmbh | Core/shell nanoparticles suitable for(f)ret-assays |
| CN104364956A (en) * | 2012-06-20 | 2015-02-18 | 丰田自动车株式会社 | Battery system, method for manufacturing battery system, and battery control apparatus |
| US20150228971A1 (en) * | 2014-02-07 | 2015-08-13 | Samsung Sdi Co., Ltd. | Positive active material, positive electrode and lithium battery including the positive active material, and method of manufacturing the positive active material |
| CN104409705A (en) * | 2014-12-20 | 2015-03-11 | 宫香娥 | Preparation method of carbon-coated germanium-doped lithium manganate composite cathode material |
| JP2018022637A (en) * | 2016-08-05 | 2018-02-08 | Tdk株式会社 | Positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery |
| CN112447967A (en) * | 2019-09-02 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, positive electrode plate and lithium ion secondary battery |
| CN113471411A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Composite coated positive electrode material and preparation method thereof |
| CN113471414A (en) * | 2020-03-31 | 2021-10-01 | 北京卫蓝新能源科技有限公司 | Lithium ion battery composite positive electrode material and preparation method and application thereof |
| CN111987303A (en) * | 2020-08-12 | 2020-11-24 | 中南大学 | Titanium germanium aluminum lithium phosphate modified high-nickel cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHAI YIFAN等: ""Structure, Raman spectra and properties of two low-epsilon(r) microwave dielectric ceramics Ca3B2Ge3O12 (B = Al, Ga)"", 《CERAMICS INTERNATIONAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114388797B (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108390022B (en) | Carbon-metal oxide composite coated lithium battery ternary positive electrode material, preparation method thereof and lithium battery | |
| CN111592052B (en) | Lithium nickel manganese oxide composite material, preparation method thereof and lithium ion battery | |
| JP6888297B2 (en) | Positive electrode active material for non-aqueous electrolyte secondary batteries and its manufacturing method | |
| CN112080800A (en) | Modification method of single crystal ternary cathode material | |
| CN110233250B (en) | Preparation method of single crystal particle ternary cathode material | |
| CN114843498A (en) | Sodium-containing oxide positive electrode material, preparation method and application thereof, positive electrode plate and application thereof | |
| CN109713251B (en) | Lithium ion battery anode material and preparation method and application thereof | |
| CN112271281B (en) | Composite cathode material, preparation method and application thereof, and lithium ion battery | |
| CN108933247B (en) | Method for preparing AZO-coated 523 single-crystal nickel-cobalt-manganese ternary positive electrode material and product | |
| CN105633384B (en) | Power lithium-ion battery positive electrode surface modification technology method | |
| JP2023532367A (en) | Lithium ion battery positive electrode active material and manufacturing method thereof | |
| CN113044891A (en) | Preparation method of surface grafting type high-voltage lithium cobaltate, surface grafting type high-voltage lithium cobaltate and application thereof | |
| CN114447309B (en) | Sodium ion doped lithium ion battery positive electrode material and preparation method thereof | |
| CN113929070A (en) | Preparation method of high-rate lithium iron phosphate cathode material | |
| CN116799186A (en) | Positive electrode material, preparation method thereof and application of positive electrode material in sodium ion battery | |
| CN109786703B (en) | Conductive ceramic oxide coated lithium ion battery anode material and preparation method thereof | |
| CN112786881A (en) | Solid-state lithium battery and preparation method thereof | |
| WO2024066809A1 (en) | Positive electrode material, preparation method therefor, positive electrode sheet, secondary battery, and electronic device | |
| CN114388797B (en) | Coated lithium ion battery ternary cathode material and preparation method and application thereof | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN116895744A (en) | Preparation method of long-cycle sodium-ion battery positive electrode material and sodium-ion battery | |
| CN115911332A (en) | Copper-manganese-based layered oxide material, preparation method, positive electrode and sodium ion battery | |
| CN115806281A (en) | Lithium manganese iron phosphate composite material, preparation method thereof and battery | |
| CN115425202A (en) | Preparation method of coated modified nickel-rich lithium ion ternary cathode material and product thereof | |
| CN115312730A (en) | Composite lithium ion battery anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |