CN114447336A - Preparation method of high-nickel ternary positive electrode material, positive electrode material and battery - Google Patents
Preparation method of high-nickel ternary positive electrode material, positive electrode material and battery Download PDFInfo
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- CN114447336A CN114447336A CN202210111923.9A CN202210111923A CN114447336A CN 114447336 A CN114447336 A CN 114447336A CN 202210111923 A CN202210111923 A CN 202210111923A CN 114447336 A CN114447336 A CN 114447336A
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- nickel ternary
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
Abstract
The invention provides a preparation method of a high-nickel ternary cathode material, a cathode material and a battery, and relates to the technical field of battery production. The preparation method of the high-nickel ternary cathode material comprises the following steps: preparing reaction base liquid, wherein the reaction base liquid comprises a high-nickel ternary material; adding pyrrole monomers into the reaction base liquid to perform pyrrole polymerization reaction to obtain a polymer; and sintering the generated polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material. Therefore, the pyrrole is polymerized in the reaction base liquid and uniformly coated on the surface of the ternary material, and is sintered in the inert gas atmosphere to be carbonized into the nitrogen-doped carbon coating layer, so that the coating effect is good, the coating is more uniform, the conductivity of the coating layer can be effectively improved, and the rate capability of the battery is improved.
Description
Technical Field
The invention relates to the technical field of battery production, in particular to a preparation method of a high-nickel ternary positive electrode material, a positive electrode material and a battery.
Background
The lithium ion battery is widely applied due to the characteristics of high energy density, long cycle service life, strong safety and the like, and the high-nickel ternary cathode material becomes a preferred cathode material of a commercial lithium ion battery by virtue of higher energy density and also becomes a development focus in the industrial field at the present stage. However, commercial lithium batteries require excellent rate capability, and the high-nickel ternary material generally needs to be improved to meet the use requirement due to poor electronic conductivity.
One of the existing methods for improving the rate capability of the high-nickel ternary material is to perform carbon coating, the existing carbon coating is mainly performed by a dry mixing-sintering method, carbon sources mainly comprise carbon powder, carbon nanotubes, organic carbon and the like, but the existing material subjected to dry carbon mixing sintering has uneven carbon coating and can affect the material performance of the battery.
Disclosure of Invention
The invention aims to provide a preparation method of a high-nickel ternary cathode material, the cathode material and a battery, which have good coating uniformity and can effectively improve the rate capability of the battery.
Embodiments of the invention may be implemented as follows:
in a first aspect, the present invention provides a preparation method of a high-nickel ternary cathode material, including:
preparing reaction base liquid, wherein the reaction base liquid comprises a high-nickel ternary material;
adding pyrrole monomers into the reaction base liquid to perform pyrrole polymerization reaction to obtain a polymer;
and sintering the generated polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
In an alternative embodiment, the step of preparing the reaction base liquid comprises:
and adding the high-nickel ternary material into a water solution and an ethanol solution, uniformly stirring, and adding an oxidant to prepare the reaction base solution.
In an alternative embodiment, the oxidizing agent is ammonium persulfate.
In an alternative embodiment, after the step of adding pyrrole monomer to the reaction base solution to perform pyrrole polymerization reaction and obtain polymer, the method further comprises:
and stirring the reaction base solution added with the pyrrole monomer for 3-5 hours.
In an optional embodiment, after the step of stirring the reaction base solution to which the pyrrole monomer is added for 3 to 5 hours, the method further includes:
the polymer in the stirred solution is filtered, washed and dried.
In an alternative embodiment, the step of sintering the polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material comprises:
and sintering the polymer in an inert gas atmosphere for 3-5 hours, and keeping the inert gas atmosphere unchanged in the sintering process to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
In an alternative embodiment, the step of sintering the polymer in an inert gas atmosphere for 3 to 5 hours further comprises:
and (3) placing the polymer in a tubular furnace with an inert gas atmosphere and sintering for 3-5 hours at the temperature of 600-700 ℃.
In an alternative embodiment, the inert gas is nitrogen.
In a second aspect, the present invention provides a positive electrode material, which is prepared by the method for preparing the high-nickel ternary positive electrode material according to any one of the foregoing embodiments.
In a third aspect, the present invention provides a battery comprising a positive electrode made of the positive electrode material according to the previous embodiment.
The preparation method of the high-nickel ternary cathode material, the cathode material and the battery provided by the embodiment of the invention have the beneficial effects that: pyrrole is polymerized in reaction base liquid and uniformly coated on the surface of the ternary material, and is sintered in an inert gas atmosphere to be carbonized into a nitrogen-doped carbon coating layer, so that the coating effect is good, the coating is more uniform, the conductivity of the coating layer can be effectively improved, and the rate capability of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a flow chart illustrating the steps of a method for preparing a high nickel ternary positive electrode material according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of rate capability provided by an embodiment of the present invention;
FIG. 3 is a SEM illustration of a carbon coated sample of FIG. 1 according to an embodiment of the present invention;
fig. 4 is a SEM schematic view of a carbon-coated sample according to an embodiment of the present invention 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined and explained in subsequent figures.
In the description of the present invention, it should be noted that if the terms "upper", "lower", "inside", "outside", etc. indicate an orientation or a positional relationship based on that shown in the drawings or that the product of the present invention is used as it is, this is only for convenience of description and simplification of the description, and it does not indicate or imply that the device or the element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention.
Furthermore, the appearances of the terms "first," "second," and the like, if any, are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
It should be noted that the features of the embodiments of the present invention may be combined with each other without conflict.
Referring to fig. 1, an embodiment of the present invention provides a method for preparing a high-nickel ternary cathode material, which is used for preparing a cathode material of a battery, and the method for preparing a high-nickel ternary cathode material provided in an embodiment of the present invention can enable a nitrogen-doped carbon source to be more uniformly coated on the surface of the high-nickel ternary material, so as to effectively improve the electronic conductivity of a coating layer, and further improve the rate capability of the battery.
It should be noted that although the high-nickel ternary material is widely used for manufacturing the battery cathode material, the conductivity is particularly poor, and therefore carbon coating is usually performed on the surface of the high-nickel ternary cathode material to improve the rate performance, whereas the carbon coating layer of the existing carbon coating process (such as dry carbon mixed sintering) is usually not uniform, which may reduce the performance of the battery. Therefore, the embodiment of the invention provides a wet carbon coating process aiming at the problem of non-uniformity of a carbon coating layer in the prior art, pyrrole is polymerized in a reaction base solution and uniformly coated on the surface of a ternary material, and the ternary material is carbonized into a nitrogen-doped carbon coating layer under the action of a nitrogen atmosphere, so that the coating effect is good, the coating is more uniform, the conductivity of the coating layer can be effectively improved, and the rate capability of a battery is improved.
The preparation method of the high-nickel ternary cathode material comprises the following steps of:
s100, preparing reaction base liquid, wherein the reaction base liquid comprises a high-nickel ternary material.
In step S100, the step of preparing a reaction base liquid includes:
adding a high-nickel ternary material into a water solution and an ethanol solution, uniformly stirring, and adding an oxidant to prepare a reaction base solution.
In this embodiment, the mixed solution of water and ethanol is a medium for the polymerization reaction of the nickel-rich ternary material and the pyrrole monomer, and the pyrrole monomer is easily soluble in ethanol, so that the nickel-rich ternary material is added into the mixed solution of water and ethanol and uniformly stirred, which is helpful for the more sufficient subsequent reaction and ensures the more uniform carbon coating.
Alternatively, the oxidizing agent is ammonium persulfate, and of course, the oxidizing agent may also be a ferric ion solution or other solution with strong oxidizing property, and is not particularly limited herein.
And S200, adding pyrrole monomers into the reaction base liquid to perform pyrrole polymerization reaction to obtain a polymer.
In this embodiment, pyrrole monomers are added into the reaction base solution and then undergo pyrrole polymerization under the action of the oxidant, and the formed polypyrrole is uniformly coated on the surface of the high-nickel ternary material, so as to form a solid polymer of the polypyrrole-coated high-nickel ternary material.
Further, the reaction base solution to which the pyrrole monomer is added is stirred for 3 to 5 hours after the pyrrole monomer is added to the reaction base solution.
In this embodiment, can stir when adding reaction base liquid, also can stir after accomplishing to add reaction base liquid, generally need slowly stir 3 ~ 5 hours to make polymerization more abundant, and make polypyrrole distribute more evenly, thereby make the polypyrrole that forms wrap more evenly on high-nickel ternary material's surface, consequently realized that the cladding effect is more even, and make the multiplying power performance of battery obtain great promotion. In addition, the polypyrrole can be completely coated on the high-nickel ternary material after being slowly stirred for 3-5 hours, and the condition that only part of the high-nickel ternary material is coated with the polypyrrole is avoided.
Further, after the step of stirring the reaction base solution to which the pyrrole monomer is added for 3 to 5 hours, the polymer in the stirred solution is filtered, washed and dried.
In this embodiment, the polymer is screened out by filtering after the completion of the stirring, and then the polymer is washed to remove the reaction solution and other impurities remaining between the polymers, to prevent the reaction solution or impurities from affecting the subsequent reaction, and finally the polymer is dried to remove water.
And S300, sintering the generated polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
In the embodiment, the polymer is sintered in an inert gas atmosphere for 3-5 hours, and the inert gas atmosphere is kept unchanged in the sintering process, so as to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
Specifically, the inert gas is nitrogen, the dried polymer is placed in a tubular furnace with a nitrogen atmosphere, sintering is carried out for 3-5 hours at the temperature of 600-700 ℃, the nitrogen atmosphere is kept unchanged in the sintering process, and after sintering is completed, the nitrogen-doped carbon-coated high-nickel ternary cathode material can be obtained.
Referring to fig. 2 to 4, fig. 2 is a graph of multiplying power of different samples according to the present invention, wherein the ordinate represents the capacity in mAh/g; the abscissa indicates the number of cycles. The common sample is a sample subjected to common carbon coating, and the carbon-coated sample is a sample prepared by a preparation method of the high-nickel ternary cathode material. Fig. 3 and 4 are electron microscopic scanning images of the carbon-coated sample, and as can be seen from fig. 3 and 4, the nitrogen-doped carbon is uniformly coated on the surface of the high-nickel ternary cathode material, and as can be seen from fig. 2 to 4, the capacities of the multiple groups of carbon-coated samples are all higher than those of the common sample, which indicates that the capacities of the carbon-coated samples under different current densities are all higher than those of the common sample, thereby showing that the rate capability of the carbon-coated sample is better.
The embodiment of the invention also provides a positive electrode material, and the positive electrode material is manufactured by using the preparation method of the high-nickel ternary positive electrode material.
The embodiment of the invention also provides a battery which can be applied to the fields of energy storage equipment, new energy automobiles, electric devices and the like. The battery includes a positive electrode made of the positive electrode material in the above embodiment.
In summary, according to the preparation method of the high-nickel ternary cathode material, the cathode material and the battery provided by the embodiments of the present invention, pyrrole is polymerized in the reaction base solution and uniformly coated on the surface of the ternary material, and is carbonized into the nitrogen-doped carbon coating layer under the action of the nitrogen atmosphere, so that the coating effect is good, the coating is more uniform, the conductivity of the coating layer can be effectively improved, and the rate capability of the battery is improved.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a high-nickel ternary cathode material is characterized by comprising the following steps:
preparing reaction base liquid, wherein the reaction base liquid comprises a high-nickel ternary material;
adding pyrrole monomers into the reaction base liquid to perform pyrrole polymerization reaction to obtain a polymer;
and sintering the generated polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
2. The method of preparing a high-nickel ternary positive electrode material according to claim 1, wherein the step of preparing a reaction base solution comprises:
and adding the high-nickel ternary material into a water solution and an ethanol solution, uniformly stirring, and adding an oxidant to prepare the reaction base solution.
3. The method for preparing a high-nickel ternary cathode material according to claim 2, wherein the oxidant is ammonium persulfate.
4. The method for preparing a high-nickel ternary positive electrode material according to claim 1, wherein the step of adding pyrrole monomer to the reaction base solution to cause pyrrole polymerization reaction and obtain a polymer further comprises:
and stirring the reaction base solution added with the pyrrole monomer for 3-5 hours.
5. The method for preparing a high-nickel ternary cathode material according to claim 4, wherein after the step of stirring the reaction base solution to which the pyrrole monomer is added for 3 to 5 hours, the method further comprises:
the polymer in the stirred solution is filtered, washed and dried.
6. The method of claim 1, wherein the step of sintering the polymer to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material comprises:
and sintering the polymer in an inert gas atmosphere for 3-5 hours, and keeping the inert gas atmosphere unchanged in the sintering process to obtain the nitrogen-doped carbon-coated high-nickel ternary cathode material.
7. The method for preparing the high-nickel ternary cathode material according to claim 6, wherein the step of sintering the polymer in an inert gas atmosphere for 3 to 5 hours further comprises:
and (3) placing the polymer in a tubular furnace with an inert gas atmosphere and sintering for 3-5 hours at the temperature of 600-700 ℃.
8. The method of claim 6, wherein the inert gas is nitrogen.
9. A positive electrode material, characterized by being produced by the method for producing a high-nickel ternary positive electrode material according to any one of claims 1 to 8.
10. A battery comprising a positive electrode made of the positive electrode material according to claim 9.
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Patent Citations (6)
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| WO2015014121A1 (en) * | 2013-07-29 | 2015-02-05 | 华为技术有限公司 | Negative active material of lithium-ion secondary battery and preparation method therefor, negative plate of lithium-ion secondary battery, and lithium-ion secondary battery |
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| CN110783564A (en) * | 2019-11-07 | 2020-02-11 | 珠海冠宇电池有限公司 | Nitrogen-doped carbon-coated ternary positive electrode material and preparation method thereof |
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