CN114057236A - Nickel-manganese binary composite positive electrode material and preparation method thereof - Google Patents
Nickel-manganese binary composite positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of battery materials, in particular to a nickel-manganese binary composite positive electrode material and a preparation method thereof, and the preparation method comprises the following steps: respectively preparing a total mixed salt solution containing nickel and manganese and a doped metal salt solution; adding the first mixed salt solution, a first complexing agent and a first precipitator into the base solution in a concurrent flow manner, and carrying out a first coprecipitation reaction to obtain a reaction solution containing initial particles; adding the doped metal solution, a second mixed salt solution, a second complexing agent and a second precipitator into the reaction solution containing the initial particles in a concurrent flow manner, and carrying out a second coprecipitation reaction to obtain a reaction solution containing target particles; then aging and solid-liquid separation are carried out to obtain a nickel-manganese binary precursor; and mixing the nickel-manganese binary precursor with a lithium source, and sintering to obtain the nickel-manganese binary composite cathode material. The nickel-manganese binary anode material prepared by the preparation method not only can keep higher capacity in a long circulation process, but also has low cost and good application prospect.
Description
Technical Field
The application belongs to the technical field of battery materials, and particularly relates to a nickel-manganese binary composite positive electrode material and a preparation method thereof.
Background
In recent years, electric vehicles with high efficiency and no pollution have been rapidly developed. The battery is used as one of the core components of the electric automobile, the performance of the battery directly influences various performance indexes of the electric automobile, and the performance of the battery directly influences the performance indexes of the battery by using the anode material as an important component of the battery, so that the performance of the anode material can be improved layer by layer on the electric automobile.
The nickel-cobalt-manganese ternary cathode material is one of the main cathode materials at present, has the characteristics of high capacity and long service life, but contains expensive cobalt metal, and is limited by the price of the cobalt metal, so that the cost of the ternary cathode material is at a disadvantage, and the wide application of the ternary cathode material in the field of electric automobiles is limited. In order to get rid of the dependence on high-valence cobalt metal, researchers seek a breakthrough on a cobalt-free nickel-manganese binary anode material. Because of the requirement of the electric automobile on the endurance mileage, people need to rely on improving the content of nickel metal in order to improve the discharge capacity, but the content of nickel metal is higher, the content of manganese metal is correspondingly reduced, so that the structural stability of the material is poor, the structural stability is further reduced, the cycle stability is further reduced, and the service life of the battery is shortened. In order to solve this problem, there is a method of obtaining an internally doped binary positive electrode material by high-temperature sintering, but the internally doped metal of the binary positive electrode material obtained by this method has a problem of non-uniform distribution.
Disclosure of Invention
The application aims to provide a nickel-manganese binary composite cathode material and a preparation method thereof, and aims to solve the technical problem of how to prepare a high-capacity and long-cycle nickel-manganese-doped binary cathode material.
In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the application provides a method for preparing a nickel-manganese binary composite positive electrode material, comprising the following steps:
respectively preparing a total mixed salt solution containing nickel and manganese and a doped metal salt solution; wherein the total mixed salt solution consists of a first mixed salt solution and a second mixed salt solution;
adding the first mixed salt solution, a first complexing agent and a first precipitator into a base solution in a concurrent flow manner, and performing a first coprecipitation reaction to obtain a reaction solution containing initial particles; the primary particles have a first size range of: the first granularity is more than 6.5 mu m and less than or equal to 8.0 mu m;
adding the doped metal solution, the second mixed salt solution, a second complexing agent and a second precipitator into the reaction solution containing the initial particles in a concurrent flow manner, and performing a second coprecipitation reaction to obtain a reaction solution containing target particles; the second size range of the target particles is: the second granularity is more than 8.0 mu m and less than or equal to 13.0 mu m;
aging the reaction liquid containing the target particles, and then carrying out solid-liquid separation to obtain a nickel-manganese binary precursor;
and mixing the nickel-manganese binary precursor with a lithium source for sintering treatment to obtain the nickel-manganese binary composite cathode material.
The preparation method of the nickel-manganese binary anode material comprises the steps of firstly co-precipitating nickel-manganese mixed salt to prepare initial particles with a certain particle size, then co-precipitating doped metal ions and the nickel-manganese mixed salt to prepare target particles with a larger particle size on the basis of the initial particles, so that formation of an externally doped nickel-manganese binary precursor can be realized, and the externally doped nickel-manganese binary precursor is subsequently mixed with a lithium source to be calcined to obtain the nickel-manganese binary composite anode material with better performance; in the process, the doped metal enters the precursor in an ionic state in the coprecipitation process, so that the dispersion effect is good, the doped metal is uniformly doped on the periphery of the particles, and the dosage of the doped metal can be greatly reduced while the doping effect is ensured. Therefore, the nickel-manganese binary anode material prepared by the preparation method not only can keep higher capacity in a long circulation process, but also has low cost and good application prospect.
In a second aspect, the present application provides a nickel-manganese binary composite positive electrode material, which is prepared by the preparation method described in the present application.
The nickel-manganese binary composite cathode material is prepared by the specific preparation method. In the preparation method, the doped metal enters the precursor in an ionic state in the coprecipitation process, so that the dispersion effect is good, and the doped metal is uniformly doped on the periphery of the particles, so that the dosage of the doped metal can be greatly reduced while the doping effect is ensured. Therefore, the nickel-manganese binary anode material has the characteristics of low cost, high capacity and long cycle.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a preparation method of a nickel-manganese binary composite positive electrode material provided in an embodiment of the present application.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
In the present application, "at least one" means one or more, "plural" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items.
It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the embodiments of the present application may be a mass unit known in the chemical industry field such as μ g, mg, g, kg, etc.
The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.
A first aspect of an embodiment of the present application provides a method for preparing a nickel-manganese binary composite positive electrode material, as shown in fig. 1, the method includes the following steps:
s01: respectively preparing a total mixed salt solution containing nickel and manganese and a doped metal salt solution; wherein the total mixed salt solution consists of a first mixed salt solution and a second mixed salt solution;
s02: adding the first mixed salt solution, a first complexing agent and a first precipitator into the base solution in a concurrent flow manner, and carrying out a first coprecipitation reaction to obtain a reaction solution containing initial particles; the first size range of the primary particles is: the first granularity is more than 6.5 mu m and less than or equal to 8.0 mu m;
s03: adding the doped metal solution, a second mixed salt solution, a second complexing agent and a second precipitator into the reaction solution containing the initial particles in a concurrent flow manner, and carrying out a second coprecipitation reaction to obtain a reaction solution containing target particles; the second size range of the target particles is: the second granularity is more than 8.0 mu m and less than or equal to 13.0 mu m;
s04: aging the reaction liquid containing the target particles, and then carrying out solid-liquid separation to obtain a nickel-manganese binary precursor;
s05: and mixing the nickel-manganese binary precursor with a lithium source, and sintering to obtain the nickel-manganese binary composite cathode material.
According to the preparation method of the nickel-manganese binary positive electrode material, firstly, the mixed salt of nickel and manganese is coprecipitated to prepare initial particles with a certain particle size, then, the mixed salt of doped metal ions and nickel and manganese is coprecipitated to prepare target particles with larger particle size on the basis of the initial particles, so that the formation of an externally doped nickel-manganese binary precursor can be realized, and the externally doped nickel-manganese binary precursor is subsequently mixed with a lithium source to be calcined to obtain the nickel-manganese binary composite positive electrode material with better performance; in the process, the doped metal enters the precursor in an ionic state in the coprecipitation process, so that the dispersion effect is good, the doped metal is uniformly doped on the periphery of the particles, and the dosage of the doped metal can be greatly reduced while the doping effect is ensured. Therefore, the nickel-manganese binary anode material prepared by the preparation method not only can keep higher capacity in a long circulation process, but also has low cost and good application prospect.
In the step S01, the total mixed salt solution is obtained by dissolving soluble nickel salt and soluble manganese salt in a solvent, and the total mixed salt solution is divided into two parts for the two-step coprecipitation reaction, that is, the total mixed salt solution is composed of a first mixed salt solution and a second mixed salt solution. Wherein, the soluble manganese salt can be selected from at least one of manganese acetate, manganese oxalate, manganese nitrate, manganese sulfate and manganese phosphate, and the soluble nickel salt can be selected from at least one of nickel chloride, nickel acetate, manganese nitrate and manganese sulfate. And the doped metal salt solution is obtained by dissolving a soluble metal salt corresponding to a doped metal used for doping in a solvent, and the doped metal salt may be a soluble metal salt corresponding to at least one of doped metals of aluminum (Al), magnesium (Mg), tungsten (W), titanium (Ti), niobium (Nb), and molybdenum (Mo).
In one embodiment, the molar ratio of nickel, manganese in the total mixed salt solution containing nickel and manganese to the doping metal in the doping metal salt solution is a: b: and c, the chemical general formula of the obtained nickel-manganese binary precursor is as follows: niaMnbXc(OH)2；
Wherein a is more than 0.5 and less than or equal to 0.98; b is more than or equal to 0.02 and less than or equal to 0.5, c is more than 0 and less than or equal to 0.05, a + b + c is 1, and X is at least one of doped metals Al, Mg, W, Ti, Nb and Mo.
In one embodiment, the total concentration of nickel and manganese in the total mixed salt solution containing nickel and manganese is 0.5-3 mol/L; the concentration of the doped metal in the doped metal salt solution is 0.1-3 mol/L. Under the concentration condition, the dispersing effect of each salt is better.
In one embodiment, the pH of the base solution is 7.5-12.5, and the concentration of ammonium ions in the base solution is 1-10 g/L. The base solution can provide a better reaction environment for the precipitation reaction.
Further, adding the first mixed salt solution, the first complexing agent and the first precipitator into the base solution in parallel, and performing a first co-precipitation reaction under conditions comprising: the temperature is 30-70 ℃, and the rotation speed is 100-500 rpm. Wherein, the first complexing agent is ammonia water, the specific concentration can be 0.2-10 mol/L, and the first precipitator is an alkali metal hydroxide solution, such as a sodium hydroxide solution, the specific concentration can be 3-15 mol/L.
Further, the doping metal solution, the second mixed salt solution, the second complexing agent and the second precipitating agent are added into the reaction solution containing the initial particles in parallel, and the conditions for carrying out the second coprecipitation reaction include: the temperature is 30-70 ℃, and the rotating speed is 100-400 rpm. Wherein the second complexing agent is ammonia water with a specific concentration of 0.2-10 mol/L, and the second precipitator is an alkali metal hydroxide solution, such as a sodium hydroxide solution, with a specific concentration of 3-15 mol/L.
The preparation process is a precursor preparation process, and in one embodiment, nickel-manganese soluble mixed salt solution is prepared according to a certain nickel-manganese metal ion molar ratio, doped metal salt solution is prepared, complexing agent ammonia water solution and precipitator alkali solution are prepared; introducing pure water, an ammonia water solution and an alkali liquor into the reaction kettle to prepare a reaction base solution; heating the reaction kettle, starting stirring, introducing inert gas, and then introducing a mixed salt solution, an ammonia water solution and an alkali liquor by using a precise metering pump to perform coprecipitation reaction; continuously stirring, keeping the temperature of the reaction kettle stable, and continuously introducing the mixed salt solution, the ammonia water solution and the alkali liquor. And stopping stirring and closing the inert gas when the liquid level in the reaction kettle is over the baffle, standing for a period of time, and then pumping out the supernatant. And continuously introducing inert gas, starting stirring, and introducing the nickel-manganese soluble mixed salt solution, the ammonia water solution and the alkali liquor. After the median diameter (D50) of the particles reaches a specific value D1 (D1 is more than 6.5 and less than or equal to 8.0 mu m), introducing a doped metal (Al, Mg, W, Ti, Nb, Mo and the like) salt solution into the reaction kettle until the median diameter (D50) of the particles reaches a target value D2 (D2 is more than 8.0 and less than or equal to 13.0 mu m), and transferring the reaction solution into an aging kettle for aging; and finally, carrying out solid-liquid separation on the aged product, washing the obtained solid particles, and then drying, sieving and demagnetizing to obtain the externally doped high nickel-manganese binary precursor. In the examples of the present application, the first particle size and the second particle size both refer to the median diameter (D50) of the particles.
In one embodiment, the temperature for mixing the nickel-manganese binary precursor and the lithium source for sintering is 500-1000 ℃. Fully grinding and mixing before sintering. Specifically, according to the mole ratio of lithium in a lithium source to metal (Me) in a nickel-manganese binary precursor, namely the total metal amount of nickel and manganese in the nickel-manganese binary precursor, of 1.0-1.3: 1, mixing and sintering.
Further, the lithium source is selected from at least one of lithium hydroxide and lithium carbonate.
In one embodiment, the preparation method of the nickel-manganese binary composite cathode material comprises the following steps:
1. nickel and manganese soluble salts are mixed according to a molar ratio a: b, preparing a mixed salt solution with the total concentration of 0.5-3 mol/L, and dividing into two parts. Preparing a doped metal solution with a molar ratio c, wherein the concentration of the doped metal is 0.1-3 mol/L.
Wherein a is more than 0.5 and less than or equal to 0.98; b is more than or equal to 0.02 and less than 0.5, c is more than 0 and less than or equal to 0.05, and a + b + c is 1.
Preparing a complexing agent and a precipitating agent: the complexing agent solution is an ammonia water solution with the concentration of 0.2-10 mol/L, and the precipitator solution is a NaOH water solution with the concentration of 3-15 mol/L.
2. Adding the base solution into the reaction kettle, heating to 30-70 ℃, keeping introducing nitrogen, controlling the rotating speed to be 100-500 rpm, adding the first mixed salt solution, the precipitator and the complexing agent into the reaction kettle in parallel, and controlling the pH, the ammonium concentration and the temperature to be stable within a target range. Wherein the pH of the base solution is 7.5-12.5, and the concentration of ammonium radicals is 1-10 g/L.
3. When the product D50 reaches the middle particle size D1 (D1 is more than 6.5 and less than or equal to 8.0 μm), additionally introducing a doped metal salt solution, keeping the doped metal salt solution and a second metal salt solution in parallel flow with a complexing agent and a precipitator, simultaneously adding the doped metal salt solution and the complexing agent into the reaction kettle, controlling the stable pH, the stable ammonium concentration and the stable temperature within a target range, and simultaneously adjusting the rotating speed of the reaction kettle to be 100-400 rpm.
4. And stopping feeding when the particle size in the reaction kettle reaches the target particle size D2 (D2 is more than 8.0 and less than or equal to 13.0 mu m), stirring for 15-30 min, aging, washing and drying to obtain the binary precursor.
5. The binary precursor and lithium salt are mixed according to the Li/Me molar ratio of 1.0-1.3: 1 mixing materials, and carrying out high-temperature sintering reaction after the materials are mixed. Wherein the high-temperature solid-phase sintering reaction temperature is 500-1000 ℃, and the externally-doped nickel-manganese binary composite anode material is obtained after sintering.
The second aspect of the embodiments of the present application provides a nickel-manganese binary composite positive electrode material, which is prepared by the above preparation method of the embodiments of the present application. In the preparation method, the doped metal enters the precursor in an ionic state in the coprecipitation process, so that the dispersion effect is good, and the doped metal is uniformly doped on the periphery of the particles, so that the dosage of the doped metal can be greatly reduced while the doping effect is ensured. Therefore, the nickel-manganese binary anode material disclosed by the embodiment of the application has the characteristics of low cost, high capacity and long cycle.
The following description will be given with reference to specific examples.
Example 1
Adding a proper amount of pure water, a NaOH solution and an ammonia water solution into a continuously stirred reaction kettle as a base solution (2000L, the pH value is 10, the ammonium ion concentration is 4g/L), taking nitrogen as a protective atmosphere, heating to 50 ℃, and adjusting the rotating speed of a stirring paddle to 250 r/min. A mixed salt solution of nickel sulfate and manganese sulfate (the total concentration of nickel and manganese is 1.8mol/L, wherein nickel is 1.44mol/L, manganese is 0.36mol/L), a sodium hydroxide solution (8mol/L) and an ammonia water solution (6mol/L) are continuously dripped into a reaction kettle which is continuously stirred by adopting a hydroxide coprecipitation method with sodium hydroxide as a precipitator and ammonia water as a complexing agent, the pH value of the solution is controlled to be 10 in the adding process of the mixed salt solution, and the concentration of ammonium ions is 4 g/L. During the continuous dropwise addition, when the D50 of the in-pot particles was 7.0 μm, an aqueous solution of sodium tungstate (0.2mol/L) was additionally fed [ at this time, the mixed salt solution, the sodium hydroxide solution, and the ammonia water were further added dropwise ] until the feeding of the solution was stopped when the in-pot particles D50 was 12.0 μm, and the reaction was completed. And finally, precipitating, aging, washing and drying to obtain the tungsten-doped high-nickel-manganese binary anode material precursor.
And (2) adding 5% of lithium in excess of the precursor of the tungsten-doped high-nickel-manganese binary positive electrode material and lithium carbonate (namely, the molar ratio of the total amount of lithium to nickel and manganese is 1.05: 1, uniformly mixing, presintering for 7h at 550 ℃, and then heating to 750 ℃ for sintering for 10h to obtain the tungsten-doped high-nickel-manganese binary anode material.
Example 2
Adding a proper amount of pure water, a NaOH solution and an ammonia water solution into a continuously stirred reaction kettle as a base solution (2000L, the pH value is 10, the ammonium ion concentration is 4g/L), taking nitrogen as a protective atmosphere, heating to 50 ℃, and adjusting the rotating speed of a stirring paddle to 250 r/min. A coprecipitation method of sodium hydroxide as a precipitator and ammonia water as a complexing agent is adopted, a mixed salt solution of nickel sulfate and manganese sulfate (the total concentration of nickel and manganese is 1.8mol/L, wherein nickel is 1.44mol/L, manganese is 0.36mol/L), a sodium hydroxide solution (8mol/L) and an ammonia water solution (6mol/L) are continuously dripped into a reaction kettle which is continuously stirred, the pH value of the solution is controlled to be 10, and the concentration of ammonium ions is 4 g/L. During the continuous dropwise addition, when the D50 of the in-pot particles was 7.5 μm, an aqueous solution of sodium molybdate (0.2mol/L) was additionally fed [ at this time, the mixed salt solution, the sodium hydroxide solution and the ammonia water were further added dropwise ] until the feeding of the solution was stopped when the in-pot particles D50 was 13.0 μm, and the reaction was terminated. And finally, precipitating, aging, washing and drying to obtain the molybdenum-doped high-nickel-manganese binary anode material precursor.
Uniformly mixing a molybdenum-externally-doped high-nickel-manganese binary positive electrode material precursor with lithium carbonate in an excess of 8% (namely, the molar ratio of the total amount of lithium to nickel and manganese is 1.08: 1, presintering for 7 hours at 550 ℃, and then heating to 900 ℃ for sintering for 10 hours to obtain the molybdenum-externally-doped high-nickel-manganese binary anode material.
Example 3
Adding a proper amount of pure water, a NaOH solution and an ammonia water solution into a continuously stirred reaction kettle as a base solution (2000L, the pH value is 10, the ammonium ion concentration is 4g/L), taking nitrogen as a protective atmosphere, heating to 50 ℃, and adjusting the rotating speed of a stirring paddle to 250 r/min. A mixed salt solution of nickel chloride and manganese sulfate (the total concentration of nickel and manganese is 1.8mol/L, wherein nickel is 1.44mol/L, manganese is 0.36mol/L), a sodium hydroxide solution (8mol/L) and an ammonia water solution (6mol/L) are continuously dripped into a reaction kettle which is continuously stirred by adopting a hydroxide coprecipitation method with sodium hydroxide as a precipitator and ammonia water as a complexing agent, the pH value of the solution is controlled to be 10, and the concentration of ammonium ions is 4 g/L. During the continuous dropwise addition, when the D50 of the in-pot particles was 8.0 μm, an aqueous solution of sodium tungstate (0.2mol/L) was additionally fed [ at this time, the mixed salt solution, the sodium hydroxide solution, and the ammonia water were further added dropwise ] until the feeding of the solution was stopped when the in-pot particles D50 was 13.0 μm, and the reaction was completed. And finally, precipitating, aging, washing and drying to obtain the tungsten-doped high-nickel-manganese binary anode material precursor.
Adding 10% of lithium in excess between a high nickel-manganese binary anode material precursor doped outside tungsten and lithium carbonate (namely, the molar ratio of the total amount of lithium to nickel-manganese is 1.1: 1, uniformly mixing, presintering for 7h at 550 ℃, and then heating to 900 ℃ for sintering for 10h to obtain the tungsten-doped high-nickel-manganese binary anode material.
Comparative example 1
The main differences between this comparative example and example 1 are: and (3) continuously dropwise adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a continuously stirred reaction kettle for reaction (the aqueous solution without sodium tungstate is introduced), stopping introducing the solution until the particles D50 in the kettle are 12.0 mu m, and finishing the reaction.
The rest of the procedure was the same as in example 1.
Comparative example 2
The main differences between this comparative example and example 2 are: and directly adding the mixed salt solution, the sodium hydroxide solution, the ammonia water solution and the aqueous solution of sodium molybdate into a reaction kettle which is continuously stirred for reaction until the particle D50 in the kettle is 13.0 mu m, and finishing the reaction.
The rest is the same as in example 2.
Comparative example 3
The main differences between this comparative example and example 3 are: and continuously dropwise adding the mixed salt solution, the sodium hydroxide solution and the ammonia water solution into a reaction kettle which is continuously stirred for reaction, stopping introducing the solution until the particle D50 in the kettle is 13.0 mu m, and finishing the reaction. And uniformly mixing the obtained precursor with sodium tungstate for doping and lithium carbonate, and sintering to obtain the tungsten-doped high-nickel-manganese binary anode material.
The rest was the same as in example 3.
Performance testing
The positive electrode materials prepared in examples 1-3 and comparative examples 1-3 were assembled into button cells and tested for electrochemical performance. Respectively and uniformly mixing the positive electrode material with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, adding a small amount of NMP (1-methyl-2 pyrrolidone), mixing to prepare slurry, uniformly coating the slurry on an aluminum foil, drying and cutting to prepare the positive electrode piece. And (3) assembling the button cell by taking the metal lithium sheet as a negative electrode, and performing electrochemical test (the charge-discharge cut-off potential is 2.7-4.25V) by adopting a blue test system.
The test results are shown in table 1 below.
TABLE 1
As can be seen from the above table, the positive electrode material obtained by the preparation method of the embodiment of the present application has significant advantages in the first efficiency and the long cycle retention rate while maintaining a high capacity in the first discharge, compared to the comparative example.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the nickel-manganese binary composite cathode material is characterized by comprising the following steps of:
respectively preparing a total mixed salt solution containing nickel and manganese and a doped metal salt solution; wherein the total mixed salt solution consists of a first mixed salt solution and a second mixed salt solution;
adding the first mixed salt solution, a first complexing agent and a first precipitator into a base solution in a concurrent flow manner, and performing a first coprecipitation reaction to obtain a reaction solution containing initial particles; the primary particles have a first size range of: the first granularity is more than 6.5 mu m and less than or equal to 8.0 mu m;
adding the doped metal solution, the second mixed salt solution, a second complexing agent and a second precipitator into the reaction solution containing the initial particles in a concurrent flow manner, and performing a second coprecipitation reaction to obtain a reaction solution containing target particles; the second size range of the target particles is: the second granularity is more than 8.0 mu m and less than or equal to 13.0 mu m;
aging the reaction liquid containing the target particles, and then carrying out solid-liquid separation to obtain a nickel-manganese binary precursor;
and mixing the nickel-manganese binary precursor with a lithium source for sintering treatment to obtain the nickel-manganese binary composite cathode material.
2. The method of claim 1, wherein the molar ratio of nickel, manganese in the total mixed salt solution containing nickel and manganese to the doping metal in the doping metal salt solution is a: b: c, the chemical general formula of the obtained nickel-manganese binary precursor is as follows: niaMnbXc(OH)2；
Wherein a is more than 0.5 and less than or equal to 0.98; b is more than or equal to 0.02 and less than or equal to 0.5, c is more than 0 and less than or equal to 0.05, a + b + c is 1, and X is at least one of doped metals Al, Mg, W, Ti, Nb and Mo.
3. The preparation method according to claim 2, wherein the total concentration of nickel and manganese in the total mixed salt solution containing nickel and manganese is 0.5 to 3 mol/L; the concentration of the doped metal in the doped metal salt solution is 0.1-3 mol/L.
4. The method according to claim 1, wherein the pH of the base solution is 7.5 to 12.5, and the concentration of ammonium ions in the base solution is 1 to 10 g/L.
5. The method of claim 1, wherein the conditions of the first co-precipitation reaction include: the temperature is 30-70 ℃, and the rotating speed is 100-500 rpm; the conditions of the second co-precipitation reaction include: the temperature is 30-70 ℃, and the rotating speed is 100-400 rpm.
6. The method according to claim 1, wherein the first and second complexing agents are aqueous ammonia, and the first and second precipitating agents are alkali metal hydroxide solutions.
7. The production method according to any one of claims 1 to 6, wherein the temperature of the sintering treatment is 500 to 1000 ℃.
8. The method of any one of claims 1-6, wherein the molar ratio of lithium in the lithium source to metal in the nickel manganese binary precursor is 1.0 to 1.3: 1.
9. the production method according to any one of claims 1 to 6, wherein the lithium source is at least one selected from the group consisting of lithium hydroxide and lithium carbonate.
10. A nickel-manganese binary composite positive electrode material, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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