CN113087024B - Preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide - Google Patents
Preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide Download PDFInfo
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Abstract
The invention belongs to the field of battery materials, and relates to a preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide. A preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide comprises the following steps: (1) preparing a feed liquid solution A: adding aluminum chloride and zirconium chloride into the cobalt chloride solution; solution B: an ammonium bicarbonate solution; (2) Preparing zirconium-aluminum co-doped cobalt carbonate by synthesis, and respectively performing suction filtration and oil removal on the solution A and the solution B; the mixture is introduced into a reaction kettle in a parallel flow manner for constant-temperature synthesis; (3) Sintering and preparing cobaltosic oxide coated with niobium oxide, and performing suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the powder with nano-grade niobium oxide, putting the mixture into a sintering furnace, sintering and sieving the mixture to obtain the coated cobaltosic oxide.
Description
Technical Field
The invention belongs to the field of battery materials, and relates to a preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide.
Background
The development of lithium ion batteries drives the development research and the commercial application of lithium cobaltate electrode materials, which also alleviates the problems of resource shortage and environmental destruction faced by human beings at present. Lithium cobaltate is used as the anode material of lithium ion batteries, and the structural performance characteristics of the lithium cobaltate are derived from the synthesis of a precursor cobaltosic oxide of the lithium cobaltate, and the lithium cobaltate synthesized at high temperature is widely applied to the traditional 3C electronic products because of higher specific capacity, better cycle performance, safety and easy preparation.
In the search for lithium cobaltate, in order to release the highest energy in the smallest space possible, the lithium cobaltate needs to be developed towards a high voltage, and more lithium ions are deintercalated under the high voltage, so that the specific capacity is greatly improved. However, the lithium deintercalation directly affects the stability and the cyclicity of the structure, and the cobalt is dissolved in the electrolyte to react, so that the safety does not meet the requirement. When the voltage is higher than 4.25V, the cycle performance of the battery is rapidly attenuated, and the hexagonal crystal phase of the lithium cobaltate material begins to be converted into a monoclinic phase. Research shows that the volume change of the material in the phase change process can simultaneously cause the change of the material performance, and the phase change is irreversible, so that the problems of capacity attenuation, damage to the internal structure, aggravation of side reaction and the like can be caused.
This limits the development of lithium cobaltate for battery materials and researchers now propose many improvements to this end, the mainstream of which is doping and cladding. Doping is to introduce other elements into crystal lattices of the material so as to optimize a bulk phase structure, inhibit phase change in the charge-discharge process and improve the cycle; and other elements are introduced into the surface layer or the shallow layer in the coating process, so that the surface interface structure is optimized, the side reaction of the surface interface is inhibited, and the effect of improving the circulation is achieved.
The structural performance of the cobaltosic oxide is improved by zirconium-aluminum co-doping, and a series of side reactions occur after the charging voltage is increased, so that the stability of a liquid-solid interface of the material is improved by selecting the coated niobium oxide, and the Nb has excellent toughness and strong stability at high temperature, so that the reaction between the later-stage material and an electrolyte is reduced, and the cycle performance of the material is improved.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide a method for preparing niobium oxide-coated zirconium-aluminum co-doped large-particle cobaltosic oxide, which solves the problems of unstable surface structure, poor cycle performance and weakened material and electrolyte reaction of lithium cobaltate materials in the prior art.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide is realized by the following steps:
(1) Preparation of feed liquid
Solution A: adding aluminum chloride and zirconium chloride into the cobalt chloride solution;
solution B: an ammonium bicarbonate solution;
(2) Synthesis preparation of zirconium-aluminum co-doped cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; the cobalt carbonate is introduced into a reaction kettle in a parallel flow manner to be synthesized at a constant temperature of 46 ℃, the PH is controlled by controlling the flow of ammonium bicarbonate, and the large-particle zirconium-aluminum co-doped cobalt carbonate material is prepared by adjusting the solid content of the slurry or synthesizing the slurry for multiple times by using seed crystals;
(3) Sintering preparation of niobium oxide coated cobaltosic oxide
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the powder with nano-grade niobium oxide, putting the mixture into a sintering furnace, sintering and sieving the mixture to obtain coated cobaltosic oxide;
the solution A and the solution B in the step (1) are prepared by pure water, the concentration of cobalt ions in the prepared solution A is 2mol/L, the concentrations of aluminum ions and zirconium ions are 0.006mol/L and 0.004mol/L respectively, and the concentration of ammonium bicarbonate in the solution B is 2.6mol/L.
The pH value of the reaction process in the step (2) is controlled between 7.1 and 7.4.
The growth process of the cobalt carbonate in the step (2) is to control the growth speed of particles by adjusting the solid content in the kettle until the cobalt carbonate particles grow to 20 mu m. The solid content in the kettle is adjusted by taking part of the slurry in the kettle, standing the slurry to remove the mother liquor, returning the slurry to the synthesis kettle to improve the solid content, or continuously synthesizing the slurry after putting part of the slurry to reduce the solid content.
The niobium oxide used in the step (3) is NbO, and the content of the added Nb element is 0.2wt%.
The cobaltosic oxide for the lithium ion battery prepared by the invention is doped with zirconium for modification so as to improve the ionic cycling performance of the cobaltosic oxide, and is compounded by adopting a cobalt-aluminum material so as to improve the specific capacity and the structural stability of the material, and meanwhile, the doped material is coated by the nanoscale niobium oxide, so that the cobaltosic oxide has higher specific capacity and cycling stability. Therefore, when the composite material is used for a lithium ion battery, the composite material has higher capacity and longer service life.
Drawings
Fig. 1 is a particle size distribution diagram of a finished product of niobium oxide coated zirconium-aluminum co-doped cobaltosic oxide, and it can be seen from comparison in the diagram that the particle size distribution of the niobium oxide coated zirconium-aluminum co-doped cobaltosic oxide powder is narrow and the uniformity is good.
FIG. 2 is an SEM image of zirconium-aluminum co-doped large-particle cobalt carbonate;
FIG. 3 is an SEM image of niobium oxide coated zirconium aluminum co-doped large-particle cobaltosic oxide.
The specific implementation mode is as follows:
example one
(1) Preparing feed liquid
Solution A: adding aluminum chloride and zirconium chloride into a cobalt chloride solution to prepare cobalt element with the concentration of 2mol/L respectively; the concentration of the zirconium element is 0.004mol/L; the concentration of the aluminum element is 0.006mol/L;
solution B: preparing an ammonium bicarbonate solution, wherein the concentration of the prepared ammonium bicarbonate is 2.6mol/L.
(2) Synthetic preparation of cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; and (3) introducing the mixed solution into a reaction kettle in a parallel flow manner to carry out synthesis at a constant temperature of 46 ℃, controlling the stirring speed and the solid content in the process, adjusting the flow rate of ammonium bicarbonate, and controlling the pH in the process to be 7.2 +/-0.1 until the mixed solution grows to 20 mu m to obtain the zirconium-aluminum co-doped cobalt carbonate material.
(3) Preparation of cobaltosic oxide by sintering
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; and then mixing the mixed material with nano-scale niobium oxide, wherein the addition of Nb is 0.2wt%, placing the mixed material into a sintering furnace, sintering, adjusting the temperature control process, setting the temperature gradient, heating to 400 ℃ at the rate of 5 ℃/min, keeping the temperature for 3h, heating to 800 ℃ at the rate of 5 ℃/min, keeping the temperature for 6h, and sieving to obtain the coated cobaltosic oxide.
Example two
(1) Preparing feed liquid
Solution A: adding aluminum chloride and zirconium chloride into a cobalt chloride solution to prepare cobalt element with the concentration of 2mol/L respectively; the concentration of the zirconium element is 0.006mol/L; the concentration of the aluminum element is 0.004mol/L;
solution B: preparing an ammonium bicarbonate solution, wherein the concentration of the prepared ammonium bicarbonate is 2.6mol/L.
(2) Synthetic preparation of cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; and (3) introducing the mixed solution into a reaction kettle in a parallel flow manner to carry out synthesis at a constant temperature of 46 ℃, and controlling the pH value in the process to be 7.2 +/-0.1 until the mixed solution grows to 20 mu m to obtain the zirconium-aluminum co-doped cobalt carbonate material.
(3) Preparation of cobaltosic oxide by sintering
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the mixed material with nano-grade niobium oxide, wherein the adding amount of niobium element is 0.2wt%, placing the mixed material into a sintering furnace, sintering, adjusting the temperature control process, setting the temperature gradient, heating to 400 ℃ at the speed of 5 ℃/min, keeping the temperature for 3h, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 6h, and sieving to obtain the coated cobaltosic oxide.
EXAMPLE III
(1) Preparing feed liquid
Solution A: adding aluminum chloride and zirconium chloride into a cobalt chloride solution to prepare cobalt element with the concentration of 2mol/L respectively; the concentration of the zirconium element is 0.005mol/L; the concentration of the aluminum element is 0.005mol/L;
solution B: preparing an ammonium bicarbonate solution with the ammonium bicarbonate concentration of 2.6mol/L.
(2) Synthetic preparation of cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; and (3) introducing the mixed solution into a reaction kettle in a concurrent flow manner to carry out synthesis at a constant temperature of 46 ℃, and controlling the pH value in the process to be 7.2 +/-0.1 until the mixed solution grows to 20 mu m to obtain the zirconium-aluminum co-doped cobalt carbonate material.
(3) Preparation of cobaltosic oxide by sintering
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; and then mixing the powder with nanoscale niobium oxide, wherein the addition of niobium element is 0.2wt%, placing the mixture into a sintering furnace, sintering, adjusting the temperature control process, setting gradient temperature rise, raising the temperature to 400 ℃ at 5 ℃/min, keeping the temperature for 3h, raising the temperature to 800 ℃ at 5 ℃/min, keeping the temperature for 6h, and sieving to obtain the coated cobaltosic oxide.
Example four
(1) Preparing feed liquid
Solution A: adding cobalt chloride to prepare the cobalt element concentration to 2mol/L without adding aluminum chloride and zirconium chloride into the solution; solution B: the ammonium bicarbonate solution has the ammonium bicarbonate concentration of 2.6mol/L.
(2) Synthetic preparation of cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; and introducing the cobalt carbonate into a reaction kettle in a parallel flow manner for synthesis at a constant temperature of 46 ℃, and controlling the pH value in the process to be 7.2 +/-0.1 until the cobalt carbonate grows to 20 mu m to obtain the undoped cobalt carbonate material.
(3) Preparation of cobaltosic oxide by sintering
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the mixed material with nano-grade niobium oxide, wherein the adding amount of niobium element is 0.2wt%, placing the mixed material into a sintering furnace, sintering, adjusting the temperature control process, setting the temperature gradient, heating to 400 ℃ at the speed of 5 ℃/min, keeping the temperature for 3h, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 6h, and sieving to obtain the coated cobaltosic oxide.
EXAMPLE five
(1) Preparation of feed liquid
Solution A: adding aluminum chloride and zirconium chloride into a cobalt chloride solution to prepare cobalt element with the concentration of 2mol/L respectively; the concentration of the zirconium element is 0.004mol/L; the concentration of the aluminum element is 0.006mol/L;
solution B: preparing an ammonium bicarbonate solution, wherein the concentration of the prepared ammonium bicarbonate is 2.7mol/L.
(2) Synthetic preparation of cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; and (3) introducing the mixed solution into a reaction kettle in a parallel flow manner to carry out synthesis at a constant temperature of 46 ℃, and controlling the pH value in the process to be 7.2 +/-0.1 until the mixed solution grows to 20 mu m to obtain the zirconium-aluminum co-doped cobalt carbonate material.
(3) Preparation of cobaltosic oxide by sintering
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; and (3) placing the material into a sintering furnace, sintering, adjusting the temperature control process, setting the gradient temperature rise, raising the temperature to 400 ℃ at the speed of 5 ℃/min, keeping the temperature for 3h, raising the temperature to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 6h, and sieving to obtain the cobaltosic oxide material.
The following table shows the laser particle size, tap density and specific surface area ratio of the niobium oxide coated zirconium-aluminum co-doped cobaltosic oxide obtained in the first to fifth examples, and the results are as follows:
| example of the implementation | Al:Zr:Nb(％) | TD(g/cm 3 ) | D10/μm | D50/μm | D90/μm | BET(m 2 /g) |
| Example one | 0.3:0.2:0.2 | 2.64 | 12.51 | 17.13 | 24.06 | 1.82 |
| Example two | 0.2:0.3:0.2 | 2.48 | 10.89 | 17.52 | 26.33 | 1.32 |
| EXAMPLE III | 0.25:0.25:0.2 | 2.53 | 11.20 | 18.11 | 28.42 | 1.75 |
| EXAMPLE four | 0:0:0.2 | 2.35 | 11.25 | 17.88 | 23.97 | 1.17 |
| Implementation plan five | 0.3:0.2:0 | 2.11 | 10.55 | 18.21 | 24.13 | 1.88 |
| Conventional Co 3 O 4 | 0:0:0 | 2.47 | 11.97 | 18.37 | 23.44 | 1.97 |
| Conventional CoCO 3 | 0:0:0 | 1.937 | 12.62 | 20.21 | 33.76 | 3.11 |
TABLE 1
The results in table 1 show that the difference in doping ratio has a greater influence on tap density, and that the tap density is lower and higher under the condition of higher Al content, which indicates that the doping of Al stabilizes the structure and makes the particles more compact, and that the tap density of cobaltosic oxide coated with niobium oxide is greatly improved compared with that of conventional cobaltosic oxide, which indicates that the coating of niobium oxide stabilizes the cobaltosic oxide structure and shrinks the cobaltosic oxide, and that the stability of the surface structure is enhanced while improving the density, which is beneficial to the extension of the cycle life of the later-stage lithium ion battery, and that the surface of the later-stage lithium ion battery is more compact and smooth as seen from the appearance of the later-stage lithium ion battery, and the later-stage high-voltage development of the material is facilitated.
As can be seen from fig. 1, the niobium oxide-coated zirconium aluminum co-doped cobaltosic oxide powder has narrow particle size distribution and good uniformity. As can be seen from FIGS. 2-3, the niobium oxide-coated zirconium-aluminum co-doped cobaltosic oxide has high sphericity, good dispersibility and smooth surface.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to limit the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (1)
1. A preparation method of niobium oxide coated zirconium-aluminum co-doped large-particle cobaltosic oxide is characterized by comprising the following steps:
(1) Preparing feed liquid
Solution A: adding aluminum chloride and zirconium chloride into the cobalt chloride solution;
solution B: an ammonium bicarbonate solution;
(2) Synthesis and preparation of zirconium-aluminum co-doped cobalt carbonate
Respectively carrying out suction filtration and oil removal on the solution A and the solution B; the cobalt carbonate is cocurrently introduced into a reaction kettle for constant-temperature synthesis, the pH is controlled by controlling the flow of ammonium bicarbonate, and the large-particle zirconium-aluminum co-doped cobalt carbonate material is prepared by adjusting the solid content of the slurry or synthesizing for multiple times by using seed crystals;
(3) Sintering preparation of niobium oxide coated cobaltosic oxide
Carrying out suction filtration, washing and drying on the doped cobalt carbonate to obtain cobalt carbonate powder doped with zirconium and aluminum; then mixing the powder with nano-grade niobium oxide, putting the mixture into a sintering furnace, sintering and sieving the mixture to obtain coated cobaltosic oxide;
the solution A and the solution B in the step (1) are prepared by pure water, the concentration of cobalt ions in the prepared solution A is 2mol/L, the concentrations of aluminum ions and zirconium ions are 0.006mol/L and 0.004mol/L respectively, and the concentration of ammonium bicarbonate in the solution B is 2.6mol/L;
the pH value of the reaction process in the step (2) is controlled between 7.1 and 7.4;
in the cobalt carbonate growth process in the step (2), the growth speed of particles is controlled by adjusting the solid content in the kettle until the cobalt carbonate particles grow to 20 mu m;
the solid content in the kettle is adjusted by taking part of slurry in the kettle, standing the slurry to remove mother liquor, returning the slurry to the synthesis kettle to improve the solid content, or continuously synthesizing the slurry after putting part of the slurry to reduce the solid content;
the niobium oxide used in the step (3) is NbO, and the content of the added Nb element is 0.2wt%;
the sintering process in the step (3) is to heat up to 400 ℃ at a speed of 5 ℃/min and preserve heat for 3h, and then heat up to 800 ℃ at a speed of 5 ℃/min and preserve heat for 6h.
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