CN111010887A - Preparation method of anode material, anode material and lithium ion battery - Google Patents
Preparation method of anode material, anode material and lithium ion battery Download PDFInfo
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- CN111010887A CN111010887A CN201880001591.0A CN201880001591A CN111010887A CN 111010887 A CN111010887 A CN 111010887A CN 201880001591 A CN201880001591 A CN 201880001591A CN 111010887 A CN111010887 A CN 111010887A
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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
- H01M4/50—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
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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
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Abstract
The invention provides a preparation method of a cathode material, which comprises the following steps: dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution; dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution; simultaneously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor; and mixing a lithium source and the coated positive electrode material precursor according to a preset lithium ratio metal ratio, and sintering to obtain the aluminum oxide coated positive electrode material. The coprecipitation aluminum hydroxide is formed by simultaneous titration for coating, so that the uniformly and firmly coated aluminum oxide coated anode material is obtained, and the coating layer is in direct contact with the electrolyte when the battery is charged and discharged, so that the dissolution of metal elements in the matrix of the anode material is effectively inhibited, and the decomposition of the electrolyte is reduced, thereby improving the rate capability and the cycle performance of the material; and the method is simple, the preparation time is short, and the energy and the cost are saved.
Description
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a positive electrode material, the positive electrode material and a lithium ion battery.
This section is intended to provide a background or context to the embodiments of the invention that are recited in the claims. The description herein is not admitted to be prior art by inclusion in this section.
The positive material coating treatment of the lithium battery is an effective measure for avoiding side reactions such as electrode material dissolution and the like, and in the practical process, the coating treatment is found to avoid adverse side reactions, and when a coating layer (such as an aluminum source) has better conductivity, the conductivity of the electrode can be improved, so that the positive material coating treatment is beneficial to the rate capability of the lithium battery. However, in the conventional coating technology, a plurality of raw materials of a precursor and a coating material are directly mechanically mixed and then subjected to heat treatment to obtain an oxide-coated positive electrode material. Wherein only one of the raw materials (such as dilute sulfuric acid and sodium metaaluminate) is always used for supplying source ions (such as aluminum) of the coating material, so that the material is wasted and the coating efficiency is low; and the coating mode is usually carried out in an organic solvent, so that the potential safety hazard of flammability and volatility exists. Meanwhile, the industrial coprecipitation method has a complex preparation process, a complexing agent needs to be added to stabilize the pH value, the aging time is long, and the introduction of more impurity ions can cause the reduction of the electrochemical performance of the material, so that the method is not suitable for preparing the high-performance battery cathode material.
Disclosure of Invention
In view of the above, there is a need for an improved method for preparing a positive electrode material, in which a coating layer is formed in situ by co-precipitating an acidic and basic coating precursor solution containing a coating source ion through simultaneous titration, and the obtained coating layer of the positive electrode material can be tightly attached to the surface of a positive electrode material substrate, and has good uniformity, simple preparation method, safe use and good electrochemical performance of a prepared lithium battery.
The technical scheme provided by the invention is as follows: a preparation method of a positive electrode material comprises the following steps:
dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution;
dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution;
synchronously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor;
and mixing a lithium source and the coated positive electrode material precursor according to a preset lithium ratio metal ratio, and sintering to obtain the aluminum oxide coated positive electrode material.
Further, the positive electrode material precursor has a composition represented by the following chemical formula: nixCoyMnz(OH)2(x+y+z＝1，0≤x≤1，0≤y≤1，0≤z≤1)。
Further, the solvent is one of water solution or ethanol solution, and the temperature of the water solution or the ethanol solution is controlled to be 25-80 ℃ in the dissolving process.
Further, stirring is simultaneously carried out during the dissolution process, and the stirring speed is 200rpm to 500 rpm.
Further, the solute of the aluminum source acidic titration solution comprises one of aluminum nitrate, aluminum sulfate and aluminum chloride, the solute of the aluminum source alkaline titration solution comprises one of sodium metaaluminate and potassium metaaluminate, and the concentration of the titration solution is 0.01mol/L-0.5 mol/L.
Further, the alkaline solution is one or a combination of a sodium hydroxide solution and a sodium metaaluminate solution.
Further, the pH value of the pretreatment solution is 8.5-10, and the pH value is stabilized to a preset value in the coprecipitation process.
Furthermore, the ratio of lithium element in the lithium source to the preset lithium ratio metal of the precursor of the coated positive electrode material is 1.00-1.20, the temperature of heat treatment in the sintering process is 550-1000 ℃, and the time of heat treatment is 3-24 h.
The invention also provides a positive electrode material which is prepared by adopting the following method steps:
dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution;
dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution;
synchronously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor;
and mixing a lithium source and the coated positive electrode material precursor according to a preset lithium ratio metal ratio, and sintering to obtain the aluminum oxide coated positive electrode material.
Further, the positive electrode material precursor has a composition represented by the following chemical formula: nixCoyMnz(OH)2(x+y+z＝1，0≤x≤1，0≤y≤1，0≤z≤1)。
Further, the solvent is one of water solution or ethanol solution, and the temperature of the water solution or the ethanol solution is controlled to be 25-80 ℃ in the dissolving process.
Further, stirring is simultaneously carried out during the dissolution process, and the stirring speed is 200rpm to 500 rpm.
Further, the solute of the aluminum source acidic titration solution comprises one of aluminum nitrate, aluminum sulfate and aluminum chloride, the solute of the aluminum source alkaline titration solution comprises one of sodium metaaluminate and potassium metaaluminate, and the concentration of the titration solution is 0.01mol/L-0.5 mol/L.
Further, the alkaline solution is one or a combination of a sodium hydroxide solution and a sodium metaaluminate solution.
Further, the pH value of the pretreatment solution is 8.5-10, and the pH value is stabilized to a preset value in the coprecipitation process.
Furthermore, the preset lithium ratio metal ratio of the lithium source to the precursor of the coated positive electrode material is 1.00-1.20, the temperature of heat treatment in the sintering process is 550-1000 ℃, and the time of heat treatment is 3-24 h.
The invention further provides a lithium ion battery which comprises a positive plate formed by pressing the positive electrode material.
Compared with the prior art, the preparation method of the cathode material provided by the invention comprises the following steps: dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution; dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution; synchronously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor; and mixing a lithium source and the coated positive electrode material precursor according to a preset lithium ratio metal ratio, and sintering to obtain the aluminum oxide coated positive electrode material. The invention adopts the simultaneous titration to form coprecipitation aluminum hydroxide for coating, and finally obtains the aluminum oxide coated anode material through sintering, and the coating layer has the characteristics of good uniformity, strong binding force and the like. The coating layer of the anode material in the prepared lithium ion battery is in direct contact with the electrolyte, so that the dissolution of the active substance of the anode material is effectively inhibited, and the decomposition of the electrolyte is reduced, thereby improving the rate capability and the cycle performance of the material. The method has the advantages of simple steps, easy control, short preparation time, energy conservation and low cost.
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a flow chart of the preparation of the positive electrode material of the present invention.
Fig. 2A is an SEM image of the positive electrode material obtained in the first and second embodiments of the present invention.
Fig. 2B is an energy spectrum of the positive electrode material obtained in the first embodiment of the present invention.
Fig. 3 is a magnification view of the positive electrode material obtained in the first and second embodiments of the present invention.
Fig. 4 is a graph showing cycle characteristics of a lithium ion battery manufactured using the cathode material shown in fig. 3.
Description of reference numerals:
none.
The following detailed description further illustrates embodiments of the invention in conjunction with the above-described figures.
So that the manner in which the above recited objects, features and advantages of embodiments of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings. In addition, the features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth to provide a thorough understanding of embodiments of the invention, and the described embodiments are merely a subset of embodiments of the invention, rather than a complete embodiment. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort belong to the protection scope of the embodiments of the present invention.
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 embodiments of the present invention belong. 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 embodiments of the invention.
The lithium ion battery has the advantages of high specific capacity, good cycle performance, good thermal stability, environmental friendliness and the like, and is widely applied to the fields of mobile electronic equipment, energy storage equipment, electric vehicles and hybrid electric vehicles. The ternary material has the advantages of high specific capacity, good safety performance, lower cost than a common lithium battery and the like, and becomes a hotspot for the research of the battery anode material, but the existing anode material is easy to generate side reaction with electrolyte during the charge and discharge process to corrode, so that metal ions are dissolved and harmful substances are generated, the performance of the lithium ion battery is seriously influenced, and the application of the lithium ion battery is limited.
The following describes in detail a method for preparing a positive electrode material provided by the present invention with reference to fig. 1.
The method of the invention comprises the following steps:
101: dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution;
wherein the content of the first and second substances,
the positive electrode material precursor has a composition represented by the following chemical formula: nixCoyMnz(OH)2(x+y+z＝1，0≤x≤1，0≤y≤1，0≤z≤1)。
The solvent is one of water solution or ethanol solution.
In the dissolving process, the temperature of the aqueous solution or the ethanol solution is controlled to be 25-80 ℃. In practice, a fixed value is used within the temperature range and is stabilized at this value ("stable" includes fluctuations within an acceptable range, such as within ± 1 ℃ of the set point).
Stirring is carried out simultaneously in the dissolving process, and the stirring speed is 200rpm-500 rpm. The allowable error is also preserved in the actual operation.
102: dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution;
wherein the content of the first and second substances,
the alkaline solution is one or a combination of a sodium hydroxide solution and a sodium metaaluminate solution.
The PH value of the pretreatment solution is 8.5-10, and the PH value is stabilized to a preset value in the coprecipitation process. The preset value is a fixed value within a preset range, such as PH 8.5, 9, 9.5, 10, etc.
103: synchronously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor;
wherein the content of the first and second substances,
the solute of the aluminum source acidic titration solution comprises one of aluminum nitrate, aluminum sulfate and aluminum chloride; the concentration is 0.01mol/L-0.5 mol/L.
The solute of the aluminum source alkaline titration solution comprises one of sodium metaaluminate and potassium metaaluminate, and the concentration is 0.01mol/L-0.5 mol/L.
104: and mixing the coated anode material precursor with a lithium source according to a preset proportion, and sintering to obtain the alumina-coated anode material.
Wherein the content of the first and second substances,
the preset lithium ratio metal ratio of the lithium source to the precursor of the coated anode material is 1.00-1.20, the temperature of heat treatment in the sintering process is 300-1000 ℃, and the time of heat treatment is 3-24 h.
The above methods are used to prepare cathode materials and lithium batteries, and the properties of the obtained products of the embodiments are characterized.
Firstly, preparing 0.05mol/L Al-source acidic titration solution, namely Al-source acidic coating precursor solution (Al acidic solution for short) for later use by using aluminum nitrate as a raw material; potassium metaaluminate is used as a raw material to prepare 0.05mol/L Al source alkaline titration solution, namely Al source alkaline coating precursor solution (Al alkaline solution for short) for later use.
Example 1
Weighing the precursor (Ni) of the positive electrode material5Co2Mn3(OH)2) Placing the mixture into a water solution with the constant temperature of 50 ℃, and stirring at the speed of 300rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 9;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 9, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equal amount of 50 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
mixing lithium carbonate and the precursor of the coated anode material according to the metal ratio of lithium to metal of 1:1.05, heating to 700 ℃ at the speed of 3 ℃/min, preserving heat for 3h, heating to 940 ℃ at the speed of 3 ℃/min, preserving heat for 12h, and obtaining the anode material coated by the aluminum oxide, namely the finished ternary material.
Example 2
Weighing the precursor (Ni) of the positive electrode material5Co2Mn3(OH)2) Placing the mixture into a water solution with the constant temperature of 50 ℃, and stirring at the speed of 300rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 10;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 10, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equal amount of 50 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
mixing lithium carbonate and the precursor of the coated anode material according to the metal ratio of lithium to metal of 1:1.05, heating to 700 ℃ at the speed of 3 ℃/min, preserving heat for 3h, heating to 940 ℃ at the speed of 3 ℃/min, preserving heat for 12h, and obtaining the anode material coated by the aluminum oxide, namely the finished ternary material.
Example 3
Weighing the precursor Ni of the anode material5Co2Mn3(OH)2Placing the mixture into a water solution with the constant temperature of 50 ℃, and stirring at the speed of 500rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 9;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 10, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equal amount of 50 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
mixing the lithium carbonate and the precursor of the coated positive electrode material according to the lithium metal ratio of 1:1.05, heating to 700 ℃ at a speed of 3 ℃/min, preserving heat for 3h, heating to 940 ℃ at a speed of 3 ℃/min, and preserving heat for 12h to obtain the aluminum oxide coated positive electrode material, namely the finished ternary material.
Example 4
Weighing the precursor Ni of the anode material5Co2Mn3(OH)2Placing the mixture into a water solution with the constant temperature of 60 ℃ and stirring at the speed of 300rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 9;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 10, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equivalent 60 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
mixing the lithium carbonate and the precursor of the coated positive electrode material according to the lithium metal ratio of 1:1.05, heating to 700 ℃ at a speed of 3 ℃/min, preserving heat for 3h, heating to 940 ℃ at a speed of 3 ℃/min, and preserving heat for 12h to obtain the aluminum oxide coated positive electrode material, namely the finished ternary material.
Example 5
Weighing the precursor Ni of the anode material5Co2Mn3(OH)2Placing the mixture into a water solution with the constant temperature of 50 ℃, and stirring at the speed of 300rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 9;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 10, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equal amount of 50 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
and mixing the lithium carbonate and the precursor of the coated positive electrode material according to the lithium metal ratio of 1:1.1, heating to 700 ℃ at a speed of 3 ℃/min, preserving heat for 3h, heating to 940 ℃ at a speed of 3 ℃/min, and preserving heat for 12h to obtain the aluminum oxide coated positive electrode material, namely the finished ternary material.
Example 6
Weighing the precursor Ni of the anode material5Co2Mn3(OH)2Placing the mixture into a water solution with the constant temperature of 50 ℃, and stirring at the speed of 300rpm to obtain a mixed solution;
dropwise adding a sodium hydroxide solution with the mass concentration of 32% to obtain a pretreatment solution with the pH value close to 9;
dropwise adding an Al acid solution into the pretreatment solution, wherein the addition amount of Al is calculated according to 0.1% of the mass of the precursor of the positive electrode material, and the dropwise adding speed is 8.5 ml/min; simultaneously, dropwise adding an Al alkaline solution into the pretreatment solution to stabilize the pH value to be close to 10, wherein the dropwise adding speed is 12.5 ml/min; dropwise adding an Al acid solution and an Al alkaline solution, then carrying out coprecipitation reaction, precipitating Al ions from different sources together to form nanoscale uniform aluminum hydroxide particles, uniformly adsorbing the particles on the surface layer of the anode material precursor particles, adding equal amount of 50 ℃ constant-temperature water after the chemical reaction is finished, stirring for half an hour, and carrying out centrifugal drying to obtain an aluminum hydroxide coated anode material precursor;
mixing the lithium carbonate and the precursor of the coated positive electrode material according to the lithium metal ratio of 1:1.05, heating to 680 ℃ at 3 ℃/min, preserving heat for 3h, heating to 960 ℃ at 3 ℃/min, and preserving heat for 15h to obtain the aluminum oxide coated positive electrode material, namely the finished ternary material.
The positive electrode materials obtained in the above examples 1 and 2 were subjected to performance tests, including tests of micro-morphology, rate capability, and cycle performance. Firstly, with reference to the photomicrograph of fig. 2A, it can be seen that the obtained coated particles of the cathode material have substantially the same size and are coated on the surfaces of the large matrix particles with the layered structure; as shown in the energy spectrum of fig. 2B, the bright spots are aluminum elements or alumina, which are uniformly and densely distributed on the surface of the particles, so that the alumina is uniformly and densely coated on the surface layer of the matrix particles. To characterize the electrical properties of the above-described cathode materials, rate performance (as shown in fig. 3) and cycle performance curves (as shown in fig. 4) were further tested. Fig. 3 shows specific capacities of the positive electrode materials of example 1 and example 2 at different rates, and the change trends of the positive electrode materials are consistent with each other. Specific capacities of the positive electrode material in example 1 at 0.1C, 0.2C, 0.5C, 1C, 2C, and 5C rates were 173mAh/g, 170mAh/g, 163mAh/g, 158mAh/g, 151mAh/g, and 139mAh/g, respectively; in example 2, the specific capacities of the positive electrode material at the rates of 0.1C, 0.2C, 0.5C, 1C, 2C and 5C are 170mAh/g, 167.5mAh/g, 162.5mAh/g, 157mAh/g, 149mAh/g and 137mAh/g, respectively, and the specific capacities at 5C of the two are about 80% of the specific capacity at 0.1C. Fig. 4 compares the cycle performance of the lithium batteries made of the cathode materials in the examples 1 and 2 at the rate of 1C, and it can be seen that the change trends of the cycle characteristic curves of the examples 1 and 2 are substantially consistent, and the specific capacity of the battery in the example 1 after being charged and discharged for 100 times is about 150.8mAh/g, which is equivalent to 96.4% of the initial specific capacity of 156.4 mAh/g; the specific capacity of the battery in the embodiment 2 is about 148.6mAh/g after the battery is charged and discharged for 100 times in a circulating way, which is equivalent to 95.2% of the initial specific capacity of 156.0mAh/g, and the battery has better circulating performance in conclusion. Further verifying that the structures and the performances of the materials obtained in the examples 3 to 6 are basically close to those of the examples 1 and 2, the method can obtain the lithium battery cathode material with better rate capability and cycle performance. In other embodiments, the solute of the acidic aluminum source solution, the solute of the alkaline aluminum source solution, and the reaction conditions (temperature, time, solvent, lithium-to-metal ratio, stirring speed, and the like) are not limited to the present embodiment.
In conclusion, the invention forms the double-component coated anode material of the composite zirconia and the alumina by simultaneously titrating two coating precursors, coprecipitating, drying, sintering and the like, wherein the composite coating inhibits the dissolution of metal ions in a matrix and reduces the decomposition of electrolyte under the combined action of the composite coating, so that the cycle performance of the prepared lithium battery is obviously improved.
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.
Claims (10)
- A preparation method of a positive electrode material is characterized by comprising the following steps: the method comprises the following steps:dissolving a precursor of the positive electrode material in a solvent to obtain a mixed solution;dropwise adding an alkaline solution into the mixed solution to obtain an alkaline pretreatment solution;synchronously dropwise adding an aluminum source acidic titration solution and an aluminum source alkaline titration solution into the pretreatment solution for coprecipitation to obtain a coated positive electrode material precursor;and mixing a lithium source and the coated positive electrode material precursor according to a preset lithium ratio metal ratio, and sintering to obtain the aluminum oxide coated positive electrode material.
- The method for producing a positive electrode material according to claim 1, characterized in that: the positive electrode material precursor has a composition represented by the following chemical formula: nixCoyMnz(OH)2(x+y+z＝1，0≤x≤1，0≤y≤1，0≤z≤1)。
- The method for producing a positive electrode material according to claim 1, characterized in that: the solvent is one of water solution or ethanol solution, and the temperature of the water solution or the ethanol solution is controlled to be 25-80 ℃ in the dissolving process.
- The method for producing a positive electrode material according to claim 3, characterized in that: stirring is carried out simultaneously during the dissolving process, and the stirring speed is 200rpm-500 rpm.
- The method for producing a positive electrode material according to claim 1, characterized in that: the solute of the aluminum source acidic titration solution comprises one of aluminum nitrate, aluminum sulfate and aluminum chloride, the solute of the aluminum source alkaline titration solution comprises one of sodium metaaluminate and potassium metaaluminate, and the concentration of the titration solution is 0.01-0.5 mol/L.
- The method for producing a positive electrode material according to claim 1, characterized in that: the alkaline solution is one or a combination of a sodium hydroxide solution and a sodium metaaluminate solution.
- The method for producing a positive electrode material according to claim 1, characterized in that: the PH value of the pretreatment solution is 8.5-10, and the PH value is stabilized to a preset value in the coprecipitation process.
- The method for producing a positive electrode material according to claim 1, characterized in that: the preset lithium ratio metal ratio of the lithium source to the precursor of the coated anode material is 1.00-1.20, the temperature of heat treatment in the sintering process is 300-1000 ℃, and the time of heat treatment is 3-24 h.
- A positive electrode material characterized in that: obtained by the process according to any one of claims 1 to 8.
- A lithium ion battery, characterized by: comprising a positive electrode sheet press-formed from the material according to claim 9.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2018/099021 WO2020029029A1 (en) | 2018-08-06 | 2018-08-06 | Preparation method for positive electrode material, positive electrode material and lithium ion battery |
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| CN111010887A true CN111010887A (en) | 2020-04-14 |
| CN111010887B CN111010887B (en) | 2022-07-08 |
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| WO2017170543A1 (en) * | 2016-03-31 | 2017-10-05 | Ｂａｓｆ戸田バッテリーマテリアルズ合同会社 | Positive-electrode active material particles for nonaqueous-electrolyte secondary cell, method for manufacturing said particles, and nonaqueous-electrolyte secondary cell |
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| CN113571694A (en) * | 2021-07-30 | 2021-10-29 | 浙江帕瓦新能源股份有限公司 | Multi-ion modified ternary material precursor and preparation method of anode material |
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