CN111825125A - Doped basic cobalt carbonate/cobalt carbonate composite precursor and preparation method and application thereof - Google Patents
Doped basic cobalt carbonate/cobalt carbonate composite precursor and preparation method and application thereof Download PDFInfo
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- 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 belongs to the field of lithium ion battery materials, and particularly relates to a doped basic cobaltous carbonate/cobaltous carbonate composite precursor as well as a preparation method and application thereof. The doped basic cobaltous carbonate/cobaltous carbonate composite precursor is flaky in primary particle appearance, the length of the primary particle is 500 nm-2 um, and the width of the primary particle is 100-500 nm; the secondary particles are formed by closely stacking flaky primary particles, and the sphericity is perfect. The composite precursor has high tap density, and lays a certain foundation for the high tap density lithium ion battery anode material precursor. In the process of synthesizing the composite precursor by a wet method, the particle size of a reaction system is expanded appropriately by stably reducing the stirring linear velocity of the reaction system, and simultaneously, flaky primary particles are closely stacked to form secondary spherical particles.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a doped basic cobaltous carbonate/cobaltous carbonate composite precursor and a preparation method and application thereof.
Background
Lithium cobaltate is the most widely used positive electrode material in the consumer electronics market because of its high material density and electrode compaction density, and the high volumetric energy density of lithium ion batteries using lithium cobaltate positive electrodes. With the increasing demand of consumer electronics, especially 5G mobile phones, on the endurance time and volume of lithium ion batteries, the development of high-voltage (4.45V or more) lithium cobaltate materials has become a focus of common attention in the scientific research community and enterprises. With the increase of the charging voltage, the lithium cobaltate material gradually has the problems of irreversible structure phase change, surface interface stability reduction, safety performance reduction and the like, and practical application of the lithium cobaltate material is limited. In general, researchers modify cobaltosic oxide, which is a precursor of a lithium cobaltate positive electrode material, by means of element doping, so as to improve the stability of the lithium cobaltosic oxide in a high-voltage charging and discharging process. In terms of element doping, the coprecipitation method is one of the most effective methods. In patent CN108011101B, the inventor strictly controls the times of kettle separation in the wet reaction process, and synthesizes cobaltosic oxide with large particle size and aluminum doping amount of 500-5000 ppm; in patent CN109411749A, the inventor divides the aluminum doping process into two stages, and adjusts the reaction temperature, the flow rate of the cobalt-aluminum mixed solution, and the doping amount of aluminum in the cobalt-aluminum mixed solution at key nodes of the two stages; in patent CN110217832A, the inventor adjusts and controls the ammonium bicarbonate addition amount and the system pH in three stages. The co-precipitation method mentioned in patent CN111082007A is used to prepare a doped cobaltosic oxide composite material whose precursor is basic aluminum carbonate cobalt/cobalt carbonate, but its primary particles are nanoparticles, and no further characterization test is performed on the electrochemical properties of the material.
From the above, many prior patents mention the preparation method of the doped cobaltosic oxide precursor, but there are basically few systematic studies on the primary particle morphology, phase structure and electrochemical properties of the doped cobaltosic oxide precursor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a doped basic cobaltous carbonate/cobalt carbonate composite precursor with better performance, better consistency and special appearance, and a preparation method and application thereof.
The solution of the invention is realized by the following steps:
a doped basic cobaltous carbonate/cobaltous carbonate composite precursor has flaky primary particles, wherein the length of the primary particles is 500 nm-2 um, and the width of the primary particles is 100-500 nm; the secondary particles are formed by closely stacking flaky primary particles, and the sphericity is perfect.
The preparation method of the doped basic cobalt carbonate/cobalt carbonate composite precursor comprises the following steps:
step S1, preparing a mixed salt solution containing cobalt metal and doped metal elements and an ammonium bicarbonate solution;
step S2, priming with 1.0-1.5mol/L ammonium bicarbonate solution, controlling the reaction temperature at 45-55 ℃, adding the mixed salt solution and the ammonium bicarbonate solution into a reaction kettle in a parallel flow manner, adjusting the flow rate of the ammonium bicarbonate solution, and controlling the pH value of the reaction system at 7.2-7.5; stirring in the reaction process, and when the granularity D50 of the reaction slurry is less than or equal to 10um, controlling the stirring linear speed of the reaction system to be 3-4 m/s; when the granularity D50 of the reaction slurry is larger than 10um, controlling the stirring linear velocity of the reaction system to be reduced by 0.2-0.5 m/s every 3-5 h;
and step S3, after the reaction is finished, filtering, cleaning and drying to obtain the doped basic cobaltous carbonate/cobaltous carbonate composite precursor.
Further, the cobalt salt in the step S1 is cobalt sulfate and/or cobalt chloride, and the concentration of the cobalt salt in the mixed solution is 1.5-2.0 mol/L; the doped metal element is at least one of aluminum, magnesium and titanium; the corresponding salts of aluminum and magnesium are sulfate or chloride respectively, and titanium is titanyl sulfate; the concentration of the doped metal elements in the mixed solution is 0.02-0.05 mol/L; the concentration of the ammonium bicarbonate solution is 2.0-3.0 mol/L.
Furthermore, the mixed salt solution and the ammonium bicarbonate solution are added into the liquid inlet pipe of the reaction kettle in a concurrent flow manner, and the liquid inlet pipe comprises a spraying device.
Based on the same inventive concept, the invention provides the application of the doped basic cobalt carbonate/cobalt carbonate composite precursor in the positive electrode material of the lithium ion battery.
The invention also provides a doped lithium ion battery anode material precursor, which is obtained by calcining the doped basic cobaltous carbonate/cobaltous carbonate composite precursor at high temperature.
Further, the calcination process comprises the steps of preserving heat for 1-2 hours at the temperature of 350-400 ℃ and preserving heat for 1-2 hours at the temperature of 720-750 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the doped basic cobaltous carbonate/cobaltous carbonate composite precursor provided by the invention has very high tap density, and lays a certain foundation for a high-tap lithium ion battery anode material precursor.
2. According to the invention, by stably reducing the stirring linear velocity of the reaction system, the particle size of the reaction system is suitably expanded, and flaky primary particles are closely stacked to form secondary spherical particles;
3. the invention can realize the regulation and control of the primary particle size of the composite precursor.
4. The invention adopts the spraying device to realize the full mixing reaction of the salt solution and the ammonium bicarbonate solution, thereby ensuring that the whole reaction system is more uniform and stable.
Drawings
FIG. 1 is a scanning electron micrograph of the material prepared in example 1.
Fig. 2 is an XRD picture of the material prepared in example 1.
FIG. 3 is a scanning electron micrograph of the material prepared in example 2.
Fig. 4 is an XRD picture of the material prepared in example 2.
FIG. 5 is a SEM image of the material prepared in example 3.
Fig. 6 is an XRD picture of the material prepared in example 3.
FIG. 7 is a scanning electron micrograph of the material prepared in comparative example 1.
Fig. 8 is an XRD picture of the material prepared in comparative example 1.
Detailed Description
The present invention will now be described in detail with reference to the drawings, which are given by way of illustration and explanation only and should not be construed to limit the scope of the present invention in any way.
Example 1:
the embodiment comprises the following steps:
step S1, preparing a cobalt-aluminum mixed salt solution by taking cobalt sulfate as a cobalt source and aluminum sulfate as an aluminum source, wherein the concentration of cobalt metal is 1.5mol/L, and the concentration of aluminum metal is 0.03 mol/L; preparing 2mol/L ammonium bicarbonate solution;
step S2, adding a certain amount of 1.5mol/L ammonium bicarbonate solution as a base solution into a 50L reaction kettle, leading the liquid level to just submerge the bottom of a stirring paddle, starting stirring, leading the stirring linear velocity to be 3 m/S, and controlling the reaction temperature of the system to be 45 ℃. Adding the mixed salt solution prepared in the step S1 and ammonium bicarbonate solution into the system in a concurrent flow manner, wherein the feeding speed of the mixed salt solution is 2.5L/h, and the ammonium bicarbonate solutionThe ammonium solution is fed into the system, and the reaction pH value of the system is controlled to be 7.40-7.50. When the particle size D50 was 10um, the linear velocity decreased by 0.2 m/s per 5h, the final particle size D50 was 18.9um, and the TD was 1.99 g/cm3. And (5) after the reaction is finished, filtering, cleaning and drying.
As seen from the electron microscope result of FIG. 1, the shape of the primary particles of the precursor synthesized by the wet method in example 1 is flake, the length of the primary particles is about 500nm to 1um, and the width is 100 nm to 200 nm. The secondary particles have perfect sphericity. The XRD picture of fig. 2 shows that the material is a basic cobalt carbonate/cobalt carbonate composite.
Example 2:
the embodiment comprises the following steps:
step S1, preparing a cobalt-aluminum mixed salt solution by taking cobalt sulfate as a cobalt source and aluminum sulfate as an aluminum source, wherein the concentration of cobalt metal is 1.8mol/L, and the concentration of aluminum metal is 0.04 mol/L; preparing 3mol/L ammonium bicarbonate solution;
step S2, adding a certain amount of 1.5mol/L ammonium bicarbonate solution as a base solution into a 50L reaction kettle, leading the liquid level to just submerge the bottom of a stirring paddle, starting stirring, leading the stirring linear velocity to be 3.5m/S, and controlling the reaction temperature of the system to be 50 ℃. And (4) adding the mixed salt solution prepared in the step (S1) and an ammonium bicarbonate solution into the system in a concurrent flow manner, wherein the feeding speed of the mixed salt solution is 3L/h, and the feeding of the ammonium bicarbonate solution controls the reaction pH value of the system to be 7.30-7.40. When the particle size D50 was 10um, the linear velocity decreased by 0.3 m/s per 5h, the final particle size D50 was 19.0um, and the TD was 2.01 g/cm3. And (5) after the reaction is finished, filtering, cleaning and drying.
From the electron microscope result shown in fig. 3, the shape of the primary particle of the precursor synthesized by the wet method in this embodiment is a sheet, the length of the primary particle is about 1 to 2um, and the width is 300 to 500 nm. The secondary particles have perfect sphericity. The XRD picture of fig. 4 shows that the material is a basic cobalt carbonate/cobalt carbonate composite.
Example 3:
the embodiment comprises the following steps:
step S1, preparing a cobalt-aluminum mixed salt solution by taking cobalt chloride as a cobalt source and aluminum chloride as an aluminum source, wherein the concentration of cobalt metal is 1.8mol/L, and the concentration of aluminum metal is 0.05 mol/L; preparing 2.5mol/L ammonium bicarbonate solution;
step S2, adding a certain amount of 1.0mol/L ammonium bicarbonate solution as a base solution into a 50L reaction kettle, leading the liquid level to just submerge the bottom of a stirring paddle, starting stirring, leading the stirring linear velocity to be 3.5m/S, and controlling the reaction temperature of the system to be 55 ℃. And (4) adding the mixed salt solution prepared in the step (S1) and an ammonium bicarbonate solution into the system in a concurrent flow manner, wherein the feeding speed of the mixed salt solution is 3.5L/h, and the feeding of the ammonium bicarbonate solution controls the reaction pH value of the system to be 7.20-7.30. When the particle size D50 was 10um, the linear velocity decreased by 0.2 m/s per 2h, the final particle size D50 was 18.2um, and the TD was 1.96 g/cm3. And (5) after the reaction is finished, filtering, cleaning and drying.
From the electron microscope result of fig. 5, the shape of the primary particle of the precursor synthesized by the wet method in this embodiment is a sheet, the length of the primary particle is about 500nm to 1.5um, and the width is 200nm to 400 nm. The secondary particles have perfect sphericity. The XRD picture of fig. 6 shows that the material is a basic cobalt carbonate/cobalt carbonate composite.
Comparative example 1:
the comparative example comprises the following steps:
step S1, preparing a cobalt-aluminum mixed salt solution by taking cobalt chloride as a cobalt source and aluminum chloride as an aluminum source, wherein the concentration of cobalt metal is 1.8mol/L, and the concentration of aluminum metal is 0.05 mol/L; preparing 3mol/L ammonium bicarbonate solution;
s2: adding a certain amount of 3mol/L ammonium bicarbonate solution serving as a base solution into a 50L reaction kettle, ensuring that the liquid level of the ammonium bicarbonate solution just exceeds the bottom of a stirring paddle, starting stirring, wherein the stirring linear speed is 2.5 m/s, and the reaction temperature of the system is controlled to be 40 ℃. And (4) adding the mixed salt solution prepared in the step (S1) and an ammonium bicarbonate solution into the system in a concurrent flow manner, wherein the feeding speed of the mixed salt solution is 3.5L/h, the feeding of the ammonium bicarbonate solution controls the reaction pH value of the system to be 7.40-7.50 until the final particle size D50 is 19.4um, and the TD is 1.69 g/cm3. And (5) after the reaction is finished, filtering, cleaning and drying.
As seen from the electron microscope results of fig. 7, the precursor primary particles synthesized by the wet process in this example are nanoparticles, and flakes exist on the surface of the secondary particles. The XRD pattern of fig. 8 shows that cobalt in the material exists as a cobalt carbonate phase.
And (3) centrifugally washing the samples synthesized by the wet method in the examples 1-3 and the comparative example 1 with hot water at the temperature of 60-80 ℃ for 2h, then calcining the samples in an atmosphere furnace at the temperature of 350 ℃ for 2h, and calcining the samples at the temperature of 720 ℃ for 2h to obtain the precursor of the doped lithium ion battery anode material. According to the same steps, the lithium cobaltate is prepared by referring to the prior art, and then the electrochemical performance of the lithium cobaltate is detected, wherein the detection results are shown in the following table 1:
TABLE 1 electrochemical Performance test Table for different samples
As can be seen from the above table, the positive electrode material prepared in the embodiment of the present invention has high specific charge capacity and first cycle efficiency, and the retention rate of the cycle capacity of the material is significantly higher than that of the comparative example. The invention lays a certain foundation for the research of the doped lithium ion battery anode material precursor, in particular to the doped cobaltosic oxide precursor. The doped cobaltosic oxide precursor prepared by the scheme of the invention has long service life and more stable performance when being used as the lithium battery anode material.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A doped basic cobaltous carbonate/cobaltous carbonate composite precursor is characterized in that primary particles are flaky, the length of the primary particles is 500 nm-2 um, and the width of the primary particles is 100-500 nm; the secondary particles are formed by closely stacking flaky primary particles, and the sphericity is perfect.
2. A method of preparing the doped basic cobalt carbonate/cobalt carbonate composite precursor of claim 1, comprising the steps of:
step S1, preparing a mixed salt solution containing cobalt metal and doped metal elements and an ammonium bicarbonate solution;
step S2, bottoming with an ammonium bicarbonate solution, controlling the reaction temperature at 45-55 ℃, adding the mixed salt solution and the ammonium bicarbonate solution into a reaction kettle in a parallel flow manner, and adjusting the flow rate of the ammonium bicarbonate solution to control the pH value of a reaction system to 7.2-7.5; stirring in the reaction process, and when the granularity D50 of the reaction slurry is less than or equal to 10um, controlling the stirring linear speed of the reaction system to be 3-4 m/s; when the granularity D50 of the reaction slurry is larger than 10um, controlling the stirring linear velocity of the reaction system to be reduced by 0.2-0.5 m/s every 3-5 h;
and step S3, after the reaction is finished, filtering, cleaning and drying to obtain the doped basic cobaltous carbonate/cobaltous carbonate composite precursor.
3. The method according to claim 2, wherein the cobalt salt in step S1 is cobalt sulfate and/or cobalt chloride, and the concentration of the cobalt salt in the mixed solution is 1.5 to 2.0 mol/L; the doped metal element is at least one of aluminum, magnesium and titanium, and the concentration of the doped metal element in the mixed solution is 0.02-0.05 mol/L.
4. The method of claim 2, wherein in step S1, the concentration of the prepared ammonium bicarbonate solution is 2.0-3.0 mol/L.
5. The method of claim 2, wherein in step S2, the concentration of the ammonium bicarbonate solution as the primer is 1.0-1.5 mol/L.
6. The method of claim 2, wherein in step S2, the solution inlet pipe for feeding the mixed salt solution and the ammonium bicarbonate solution into the reaction kettle comprises a spraying device.
7. Use of a doped basic cobalt carbonate/cobalt carbonate composite precursor according to claim 1 or prepared according to any one of claims 2 to 6 in a positive electrode material for a lithium ion battery.
8. The doped lithium ion battery anode material precursor is characterized in that the doped basic cobaltous carbonate/cobaltous carbonate composite precursor is obtained by high-temperature calcination.
9. The precursor of the doped lithium ion battery positive electrode material according to claim 8, wherein the calcination process comprises heat preservation at 350-400 ℃ for 1-2 h and at 720-750 ℃ for 1-2 h.
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| CN112652751A (en) * | 2020-12-23 | 2021-04-13 | 荆门市格林美新材料有限公司 | Precursor for lithium ion battery with double-layer structure, positive electrode material and preparation method |
| CN114873653A (en) * | 2022-05-11 | 2022-08-09 | 金驰能源材料有限公司 | Basic cobalt carbonate and preparation method thereof |
| WO2024060542A1 (en) * | 2022-09-19 | 2024-03-28 | 广东邦普循环科技有限公司 | Preparation method for rare earth element-doped cobalt carbonate and use thereof |
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