CN114573042A - High-element-content uniformly-doped lithium cobalt oxide precursor and preparation method thereof - Google Patents

High-element-content uniformly-doped lithium cobalt oxide precursor and preparation method thereof Download PDF

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CN114573042A
CN114573042A CN202210274768.2A CN202210274768A CN114573042A CN 114573042 A CN114573042 A CN 114573042A CN 202210274768 A CN202210274768 A CN 202210274768A CN 114573042 A CN114573042 A CN 114573042A
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lithium cobaltate
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曾雷英
范勇
谢文彬
叶文虎
刘煜旻
张见
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Xiamen Xiaw New Energy Materials Co ltd
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Abstract

The invention relates to a high-content element uniformly-doped lithium cobaltate precursor and a preparation method thereof, wherein the structural formula of the lithium cobaltate precursor is CoxMyO4Wherein x is more than or equal to 0.95 and less than 1, y is more than 0 and less than or equal to 0.05, M represents doped metal, the crystal system is a cubic crystal system, the space group is F-43M, the unit cell parameter a value of the lithium cobaltate precursor is between 8.07 and 8.12, and the true density is between 6.02g/cm3And 6.10g/cm3In the meantime.

Description

High-element-content uniformly-doped lithium cobalt oxide precursor and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-content element uniformly-doped lithium cobaltate precursor and a preparation method thereof.
Background
In the lithium ion battery technology, the lithium cobaltate material has the advantages of high energy storage density, high power density, good cycle performance, small self-discharge, no memory effect, good safety, environmental friendliness and the like, and has a difficult-to-replace status in the 3C and portable fields. However, as the demand of people increases, the demand of lithium cobaltate materials is also increasing, especially the stability of the lithium cobaltate materials under high voltage and high temperature.
In order to realize the stability of the lithium cobaltate material under high voltage and high temperature, the purpose of stabilizing the material structure can be realized by doping effective elements. The key step of the method for achieving the effect is how to realize effective and uniform doping of the doping elements into the lithium cobaltate bulk phase. However, with the increase of the content of the doping element, the conventional method has a limited means for doping uniformity, and the introduction of the doping element in the precursor preparation process is a good solution to the above problems. Compared with a lithium cobaltate finished product, the lithium cobaltate precursor has the characteristics of smaller primary particles, loose appearance, liquid-phase introduction of elements and the like, so that a scheme of high-content doping is easier to realize.
However, the current research on the precursor materials only remains on the basis of how to realize high doping, and meanwhile, the evaluation on the uniformity of the materials is mainly to perform a qualitative analysis and judgment on the doping effect of part of particles through electron microscopy. On the other hand, whether the element is doped into the lattice structure or is merely uniformly distributed on the surface of the precursor as a mixture cannot be judged by a characterization means. This problem causes erroneous judgment of the material performance, which makes the evaluation of the lithium cobaltate precursor and the evaluation of the electrochemical performance of lithium cobaltate disjointed, and accurate judgment from structure to performance cannot be realized.
For example, patent publication No. CN108011101A discloses a method for preparing aluminum-doped cobaltosic oxide with uniform large particle size, which provides cobaltosic oxide with uniform aluminum doping, large particle size and uniform particle size distribution. The method sets parameters in principle, and prevents aluminum compounds from being separated out and aggregated independently, thereby realizing the uniform distribution of aluminum elements in the cobaltosic oxide. However, the EDS data in the patent only indicates that the doping is uniform, and whether the doping elements enter the lattice structure cannot be represented.
For example, patent publication No. CN108373175A discloses an aluminum-doped cobaltosic oxide, and a preparation method and application thereof, and provides a preparation method of an aluminum-doped cobaltosic oxide, in which a mixed solution of an aluminum salt solution, a precipitant solution and an aluminum salt complexing agent is fed in a cocurrent manner, so as to overcome the problem of large difference in the sedimentation rate of various elements in the process of preparing the aluminum-doped cobaltosic oxide by a liquid-phase precipitation method, and to realize uniform distribution of each element in the prepared material. However, the operation is complicated, and the uniformity and effectiveness of aluminum doping are not characterized.
Disclosure of Invention
The invention aims to provide a lithium cobaltate precursor with high content of elements and uniform doping.
The specific scheme is as follows:
a high-element-content uniformly-doped lithium cobaltate precursor is characterized in that: the structural formula of the lithium cobaltate precursor is CoxMyO4Wherein x is more than or equal to 0.95 and less than 1, y is more than 0 and less than or equal to 0.05, M represents doped metal, the crystal system is a cubic crystal system, the space group is F-43M, the unit cell parameter a value of the lithium cobaltate precursor is between 8.07 and 8.12, and the true density is between 6.02g/cm3And 6.10g/cm3In the meantime.
Furthermore, the doped metal is one or more of Mg, Al, Zr, La, Y, Ni, Mn, Cr, V and Ti.
Further, the total content of the doped metal is 5000ppm-15000 ppm.
The invention also provides a preparation method of the high-content element uniformly-doped lithium cobaltate precursor, which comprises the following steps of:
1) adding water into cobalt salt to prepare a cobalt solution, doping metal salt to prepare a metal solution, and preparing alkali required by precipitation into an alkali solution;
2) adding deionized water and an alkali solution into a seed crystal kettle, uniformly stirring, heating to a first temperature to prepare a first base solution, introducing a cobalt solution, the alkali solution and an additive metal solution into a reaction kettle, precipitating at the first temperature, and controlling the pH value to prepare a cobalt carbonate seed crystal;
3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a long kettle, adding deionized water and an alkali solution, uniformly stirring, heating to a second temperature higher than the first temperature to prepare a second base solution, introducing the cobalt solution, the alkali solution and an additive metal solution into the reaction kettle, precipitating at the second temperature, and controlling the pH value to obtain a cobalt carbonate finished product;
4) after the precipitation is finished, performing solid-liquid separation on the materials in the long kettle, and washing with deionized water to obtain a cobalt carbonate finished product;
5) the cobalt carbonate is subjected to two-stage calcination in an oxygen-enriched atmosphere, the first stage is low-temperature calcination, and the second stage is high-temperature calcination to obtain a high-compaction lithium cobaltate precursor, namely the high-tap spheroidal cobaltosic oxide;
6) after the prepared cobaltosic oxide is tested and refined by XRD, the value of the unit cell parameter a is between 8.06 and 8.12, and the true density is between 6.02g/cm3And 6.10g/cm3The total content of doped metal is 5000ppm-15000 ppm.
Further, the precipitation temperature in the step 2 is 30-40 ℃, and the precipitation temperature in the step 3 is 45-55 ℃.
Further, the pH value of the precipitate in the step 2 is 7.0-8.0, and the pH value of the precipitate in the step 3 is 7.0-7.5.
Further, the pH value of the first base solution in the step 2 is 7.5-8.5; and the pH value of the second base solution in the step 3 is 7.8-8.3.
Further, the alkalinity of the first base solution in the step 2 is 0.25-0.35 mol/L; the alkalinity of the second base solution in the step 3 is 0.2-0.3 mol/L.
Further, in the step 2, the stirring speed is 190-230 rpm; the stirring speed in the step 3 is 220-280 rpm.
Further, the granularity of the seed crystal of the cobalt carbonate seed crystal prepared in the step 2 is 7-12 mu m; and (4) the granularity of the cobalt carbonate finished product prepared in the step (3) is 15-22 mu m.
Further, the flow rate of the cobalt salt in the step 3 is 60-70L/h.
Further, in the step 5, the low-temperature calcination temperature of the first section is 250-500 ℃; in the step 5, the temperature of the second-stage high-temperature calcination is 700-850 ℃.
Compared with the prior art, the high-content element uniformly-doped lithium cobaltate precursor and the preparation method thereof provided by the invention have the following advantages: the lithium cobaltate precursor provided by the invention takes the unit cell parameters and the true density as a scheme for macroscopically measuring the tetracobalt segregation, and can further prove the doping uniformity of the lithium cobaltate precursor.
The preparation method provided by the invention adopts low-temperature precipitation in the first stage and normal-temperature high-flow precipitation in the second stage, so that the low temperature in the first stage can reduce the precipitation rate difference between metal doped ions and Co, the uniformity of metal doping in the early stage is ensured, the secondary nucleation risk can be reduced by normal-temperature precipitation in the later stage, and the high-flow feeding is favorable for improving the reaction rate, refining primary particles and further improving the doping uniformity.
Drawings
Fig. 1 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate precursor obtained in example 1.
Fig. 2 shows a single crystal powder diffraction (XRD) pattern of the lithium cobaltate precursor obtained in example 1.
Fig. 3 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate precursor obtained in example 2.
Fig. 4 shows a single crystal powder diffraction (XRD) pattern of the lithium cobaltate precursor obtained in example 2.
Fig. 5 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate precursor obtained in example 3.
Fig. 6 shows a single crystal powder diffraction (XRD) pattern of the lithium cobaltate precursor obtained in example 3.
Fig. 7 shows a Scanning Electron Microscope (SEM) image and an elemental distribution diagram of the lithium cobaltate precursor obtained in the comparative example.
Fig. 8 shows a single crystal powder diffraction (XRD) pattern of the lithium cobaltate precursor obtained in the comparative example.
Detailed Description
The invention aims to provide a lithium cobaltate precursor material with total content of doping elements of 5000ppm-15000ppm, uniform doping elements and effective entering crystal lattices, wherein the crystal system is a cubic crystal system, the space group is F-43m, the unit cell parameter a value of the lithium cobaltate precursor material is between 8.07 and 8.12, and the true density is 6.02g/cm3And 6.10g/cm3The structural formula of the lithium cobaltate precursor material is CoxMyO4Wherein x is more than or equal to 0.95 and less than 1, Y is more than 0 and less than or equal to 0.05, and M represents doped metal and is one or more of Mg, Al, Zr, La, Y, Ni, Mn, Cr, V and Ti. When the unit cell parameter a of the a axis of the lithium cobaltate precursor material is in the range of 8.07 to 8.12, the true density is between 6.02g/cm3And 6.10g/cm3In the meantime, it can be considered that the doping elements uniformly and effectively enter the lithium cobaltate precursor.
The lithium cobaltate precursor material is prepared by the following steps:
1) adding water into cobalt salt to prepare a cobalt solution, doping metal salt to prepare a metal solution, and preparing alkali required by precipitation into an alkali solution;
2) adding deionized water and an alkali solution into a seed crystal kettle, uniformly stirring, heating to raise the temperature to prepare a first base solution, introducing a cobalt solution, the alkali solution and an additive metal solution into a reaction kettle through a metering pump for precipitation, and controlling the pH value to prepare cobalt carbonate seed crystals;
3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a long kettle, adding deionized water and an alkali solution, uniformly stirring, heating, raising the temperature, preparing to obtain a second base solution, introducing the cobalt solution, the alkali solution and an additive metal solution into the reaction kettle through a metering pump for precipitation, and controlling the pH value to obtain a cobalt carbonate finished product;
4) after the precipitation is finished, transferring the materials in the long kettle to an aging tank, beating the materials to a centrifugal machine for solid-liquid separation, and washing the materials by deionized water to obtain a cobalt carbonate finished product;
5) the cobalt carbonate is subjected to two-stage calcination in an oxygen-enriched atmosphere rail kiln, wherein the first stage is low-temperature calcination, and the second stage is high-temperature calcination to obtain a high-compaction lithium cobaltate precursor, namely the high-tap spheroidal cobaltosic oxide.
6) The crystal system of the prepared cobaltosic oxide is a cubic crystal system, the space group is F-43m, and the value of a unit cell parameter a is measured to be between 8.06 and 8.12 and the true density is measured to be 6.02g/cm after XRD test and refinement3And 6.10g/cm3Between 5000ppm and 15000ppm of doping elements.
In the preparation process of the lithium cobaltate precursor material, the prepared lithium cobaltate precursor can have better quality when one or more of the following conditions are met:
the concentration of the cobalt solution is 100g/L-150 g/L;
the metal salt solution, wherein the metal is one or more of Mg, Al, Zr, La, Y, Ni, Mn, Cr, V and Ti;
the metal concentration of the doped metal salt is 10g/L-40 g/L;
the alkali solution is an aqueous solution of ammonium bicarbonate or sodium carbonate;
the concentration of the alkali solution is 130-240 g/L;
the PH value of the first base solution in the step 2 is 7.5-8.5;
in the step 2, the alkalinity of the first base solution is 0.25-0.35 mol/L;
the precipitation temperature in the step 2 is 30-40 ℃;
in the step 2, the stirring speed is 190-230 rpm;
the pH value of the precipitate in the step 2 is 7.0-8.0.
The granularity of the seed crystal of the cobalt carbonate seed crystal prepared in the step 2 is 7-12 mu m;
the pH value of the second base solution in the step 3 is 7.8-8.3;
the alkalinity of the second base solution in the step 3 is 0.2-0.3 mol/L;
the precipitation temperature in the step 3 is 45-55 ℃;
the stirring speed in the step 3 is 220-280 rpm;
in the step 3, the cobalt salt flow is 60-70L/h;
the PH value of the precipitate in the step 3 is 7.0-7.5;
the granularity of the cobalt carbonate finished product prepared in the step 3 is 15-22 mu m;
step 4, controlling the temperature of the deionized water to be 30-60 ℃;
step 5, the low-temperature calcination temperature of the first section is 250-500 ℃;
step 5, the temperature of the second-stage high-temperature calcination is 700-850 ℃;
in the XRD test used in the step 6, the selected target is a copper target, and the test step length is 0.01 ℃;
the refining method used in the step 6 is to use a Rietveld structure refining method to carry out fitting refining on the data and use EVA and TOPAS software to carry out data analysis.
The preparation method adopts a cobalt carbonate system to prepare the cobaltosic oxide, distinguishes the seed crystal stage and the growth stage, sets different process parameters to control the precipitation rate of each stage, reduces the precipitation rate difference among elements and realizes the uniform and effective doping of the doping elements. The precipitation temperature is lower in the seed crystal stage, the crystallization rate is slower, and the cobalt carbonate crystal form is complete; while at low temperature, Co2+The precipitation rate of the element and the doped element is slower, so that the two elements can be synchronously precipitated, and the element is doped into a lattice structure. The precipitation temperature and the cobalt salt feeding amount are increased in the growth stage, the precipitation temperature is increased, the risk of growing small particles can be reduced, and the preparation of a large particle precursor with narrow particle size distribution is facilitated; meanwhile, the supersaturation degree in a reaction system can be improved by improving the flow, the precipitation rate difference of each element is reduced, and Co is favorably precipitated2+And the metal ions are precipitated together with the doping metal ions to realize uniform and effective doping.
Research shows that the performance of a lithium cobaltate precursor material is related to segregation and also related to unit cell parameters of the material, and due to nonuniform doping, defect points are increased, and the unit cell parameters are influenced finally. On the other hand, the true density can well represent whether the material is segregated or not in a uniform manner, so that the segregation degree of the cobaltosic oxide material can be analyzed after the true density and the non-uniform density are combined. Therefore, the method takes the unit cell parameters and the true density as a scheme for macroscopically determining the tetracobalt segregation, and compared with the scheme that the existing ICP (inductively coupled plasma) evaluates the content of a macrostructure or the EDS (electro-deposition) evaluates the microstructure, the method has stronger sampling representativeness and can better illustrate the effectiveness and uniformity of doping.
Example 1
Step 1: preparing raw materials. Preparing a cobalt chloride solution with a metal concentration of 100g/L, an ammonium bicarbonate solution with an ammonium bicarbonate concentration of 130g/L and an aluminum sulfate solution with a metal concentration of 10g/L for later use.
Step 2: and (4) preparing cobalt carbonate seed crystals. Adding deionized water and an ammonium bicarbonate solution into a reaction kettle, and heating to 30 ℃ to obtain a first base solution with a pH value of 7.55 and an alkalinity of 0.252 mol/L. Stirring speed is 190rpm, then a metering pump of cobalt chloride, ammonium bicarbonate and aluminum sulfate liquid is started to start feeding, the cobalt chloride flow is 50L/h, the aluminum sulfate flow is 5L/h, and the ammonium bicarbonate flow is adjusted to control the PH value of the reaction kettle to be 7.0. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the granularity of the cobalt carbonate seed crystal reaches 12 mu m, the precipitation is finished.
And step 3: and (5) preparing a cobalt carbonate finished product. And (3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a reaction kettle, adding deionized water and an ammonium bicarbonate solution to prepare a second base solution with the pH value of 7.82 and the alkalinity of 0.202mol/L, stirring at the rotating speed of 220rpm, heating to the temperature of 45 ℃ in the reaction kettle, starting a metering pump for feeding cobalt chloride, ammonium bicarbonate and aluminum sulfate feed liquid, wherein the cobalt chloride flow is 60L/h, the aluminum sulfate flow is 6L/h, and the pH value of the reaction kettle is controlled to be 7.0 by adjusting the ammonium bicarbonate flow. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the cobalt carbonate particle size reaches 20 μm, the precipitation is finished.
And 4, step 4: and washing the cobalt carbonate finished product. And (3) washing the cobalt carbonate by adopting a centrifugal machine, wherein the washing water is deionized water with the temperature of 30 ℃, and the washing time is 30 min. And dehydrating after washing to obtain a cobalt carbonate semi-finished product.
And 5: and calcining the cobalt carbonate finished product. And calcining the cobalt carbonate finished product by adopting an orbital kiln for 4h at 500 ℃ and then for 1.5h at 850 ℃ to obtain the aluminum-doped lithium cobaltate precursor.
Example 2
Step 1: preparing raw materials. Preparing a cobalt chloride solution with the metal concentration of 150g/L, a sodium carbonate solution with the metal concentration of 240g/L and a lanthanum chloride solution with the metal concentration of 40g/L for later use.
Step 2: and (4) preparing cobalt carbonate seed crystals. Adding deionized water and a sodium carbonate solution into a reaction kettle, and heating to the temperature of 40 ℃ in the reaction kettle to obtain a base solution with the pH value of 8.44 and the alkalinity of 0.347 mol/L. Stirring at 230rpm, starting a metering pump for feeding cobalt chloride, sodium carbonate and lanthanum chloride liquid, wherein the cobalt chloride flow is 50L/h, the lanthanum chloride flow is 1.87/h, and the sodium carbonate flow is adjusted to control the pH value of the reaction kettle to be 8.0. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the particle size of the cobalt carbonate seed crystal reaches 7 mu m, the precipitation is finished.
And step 3: and (5) preparing a cobalt carbonate finished product. Putting part of the cobalt carbonate seed crystals obtained in the step 2 into a reaction kettle, adding deionized water and a sodium carbonate solution to prepare a base solution with the pH value of 8.25 and the alkalinity of 0.297mol/L, stirring at the rotating speed of 280rpm, heating to the temperature of 55 ℃ in the reaction kettle, starting a metering pump for feeding cobalt chloride, sodium carbonate and lanthanum chloride feed liquid, wherein the cobalt chloride flow rate is 70L/h, the lanthanum chloride flow rate is 2.63L/h, and the pH value of the reaction kettle is controlled to be 7.5 by adjusting the sodium carbonate flow rate. And positive pressure micropores are adopted in the precipitation process to concentrate the slurry. When the cobalt carbonate particle size reached 17 μm, the precipitation was complete.
And 4, step 4: and washing the cobalt carbonate finished product. And (3) washing the cobalt carbonate by using a centrifugal machine, wherein the washing water is deionized water at 60 ℃, and the washing time is 30 min. And dehydrating after washing to obtain a cobalt carbonate semi-finished product.
And 5: and calcining the cobalt carbonate finished product. And calcining the cobalt carbonate finished product by adopting an orbital kiln for 4 hours at 250 ℃ and then 1.5 hours at 700 ℃ to obtain the lanthanum-doped lithium cobaltate precursor.
Example 3
Step 1: preparing raw materials. Preparing a cobalt chloride solution with a metal concentration of 125g/L, an ammonium bicarbonate solution with an ammonium bicarbonate concentration of 185g/L and an aluminum nitrate solution with a metal concentration of 25g/L for later use.
Step 2: and (4) preparing cobalt carbonate seed crystals. Adding deionized water and an ammonium bicarbonate solution into a reaction kettle, and heating to the temperature of 35 ℃ in the reaction kettle to obtain a base solution with the pH value of 8.03 and the alkalinity of 0.311 mol/L. Stirring speed 210rpm, then starting a metering pump for cobalt chloride, ammonium bicarbonate and aluminum nitrate feed liquid to start feeding, wherein the cobalt chloride flow is 50L/h, the aluminum nitrate flow is 3.5L/h, and the ammonium bicarbonate flow is adjusted to control the pH value of the reaction kettle to be 7.5. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the granularity of the cobalt carbonate seed crystal reaches 10 mu m, the precipitation is finished.
And step 3: and (5) preparing a cobalt carbonate finished product. And (3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a reaction kettle, adding deionized water and an ammonium bicarbonate solution to prepare a base solution with the pH value of 7.97 and the alkalinity of 0.252mol/L, stirring at the rotating speed of 250rpm, heating to the temperature of the reaction kettle of 50 ℃, starting a metering pump for feeding cobalt chloride, ammonium bicarbonate and aluminum nitrate solution, wherein the cobalt chloride flow is 65L/h, the aluminum nitrate flow is 4.55L/h, and the pH value of the reaction kettle is controlled to be 7.25 by adjusting the ammonium bicarbonate flow. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the cobalt carbonate particle size reaches 20 μm, the precipitation is finished.
And 4, step 4: and washing the cobalt carbonate finished product. And (3) washing the cobalt carbonate by using a centrifugal machine, wherein the washing water is deionized water with the temperature of 45 ℃, and the washing time is 30 min. And dehydrating after washing to obtain a cobalt carbonate semi-finished product.
And 5: and calcining the cobalt carbonate finished product. And calcining the cobalt carbonate finished product by adopting an orbital kiln for 4h at 380 ℃ and then for 1.5h at 780 ℃ to obtain the aluminum-doped cobaltosic oxide.
Comparative example
Step 1, raw material preparation. Preparing a cobalt chloride solution with a metal concentration of 125g/L, an ammonium bicarbonate solution with an ammonium bicarbonate concentration of 185g/L and an aluminum nitrate solution with a metal concentration of 25g/L for later use.
Step 2: and (4) preparing cobalt carbonate seed crystals. Adding deionized water and an ammonium bicarbonate solution into a reaction kettle, and heating to 50 ℃ to obtain a base solution with a pH value of 8.02 and an alkalinity of 0.218 mol/L. Stirring speed is 170rpm, then a metering pump of feed liquid of cobalt chloride, ammonium bicarbonate and aluminum nitrate is started to start feeding, the flow rate of cobalt chloride is 50L/h, the flow rate of aluminum nitrate is 3.5L/h, and the flow rate of ammonium bicarbonate is adjusted to control the pH value of the reaction kettle to be 7.0. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the granularity of the cobalt carbonate seed crystal reaches 15 mu m, the precipitation is finished.
And step 3: and (5) preparing a cobalt carbonate finished product. And (3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a reaction kettle, adding deionized water and an ammonium bicarbonate solution to prepare a base solution with the pH value of 8.13 and the alkalinity of 0.202mol/L, stirring at the rotating speed of 200rpm, heating to the temperature of the reaction kettle of 50 ℃, starting a metering pump for feeding cobalt chloride, ammonium bicarbonate and aluminum nitrate solution, wherein the cobalt chloride flow is 50L/h, the aluminum nitrate flow is 3.5L/h, and the pH value of the reaction kettle is controlled to be 7.0 by adjusting the ammonium bicarbonate flow. And the precipitation process adopts positive pressure micropores to concentrate the slurry. When the cobalt carbonate particle size reaches 20 μm, the precipitation is finished.
And 4, step 4: and washing the cobalt carbonate finished product. And (3) washing the cobalt carbonate by using a centrifugal machine, wherein the washing water is deionized water with the temperature of 45 ℃, and the washing time is 30 min. And dehydrating after washing to obtain a cobalt carbonate semi-finished product.
And 5: and calcining the cobalt carbonate finished product. And calcining the cobalt carbonate finished product by adopting an orbital kiln for 4h at 380 ℃ and then for 1.5h at 780 ℃ to obtain the aluminum-doped cobaltosic oxide.
The scanning electron micrographs and XRD patterns of the doped cobaltosic oxide prepared in examples 1-3 and comparative examples are shown in fig. 1-8. Wherein a in fig. 1 is a scanning electron microscope image of the aluminum-doped lithium cobaltate precursor obtained in example 1, b in fig. 1 is a distribution diagram of an aluminum element in the aluminum-doped lithium cobaltate precursor obtained in example 1, and fig. 2 is an XRD image of the aluminum-doped lithium cobaltate precursor obtained in example 1. Fig. 3 a is a scanning electron micrograph of the lanthanum-doped lithium cobaltate precursor obtained in example 2, fig. 3 b is a distribution diagram of lanthanum element in the lanthanum-doped lithium cobaltate precursor obtained in example 2, and fig. 4 is an XRD chart of the lanthanum-doped lithium cobaltate precursor obtained in example 2. Fig. 5a is a scanning electron micrograph of the aluminum-doped cobaltosic oxide obtained in example 3, fig. 5 b is a distribution diagram of an aluminum element in the aluminum-doped cobaltosic oxide obtained in example 3, and fig. 6 is an XRD diagram of the aluminum-doped cobaltosic oxide obtained in example 3. Fig. 7 a is a scanning electron micrograph of the aluminum-doped tricobalt tetraoxide prepared by the comparative example, fig. 7 b is a distribution diagram of an aluminum element in the aluminum-doped tricobalt tetraoxide prepared by the comparative example, and fig. 8 is an XRD pattern of the aluminum-doped tricobalt tetraoxide prepared by the comparative example.
As can be seen from the scanning electron microscope images and the XRD patterns of examples 1 to 3, the lithium cobaltate precursor with high content of elements and uniform doping can be obtained by the preparation method provided by the present invention, and the doping uniformity of the aluminum element in the comparative example is poor.
The XRD data of examples 1 to 3 and comparative example were subjected to fitting refinement using Rietveld structure refinement method, and data analysis using EVA, TOPAS software, to obtain XRD refinement data as shown in table 1 below.
Particle size (. mu.m) Al(ppm) La(ppm) True density Cell parameter a
Example 1 17.234 7185 / 6.0364 8.0841725
Example 2 15.549 / 7059 6.0643 8.0842747
Example 3 17.382 10468 / 6.0283 8.0843103
Comparative example 17.132 10085 / 6.1342 8.0632575
TABLE 1 XRD refinement data for examples 1-3 and comparative examples
From Table 1, it can be obtained that the true density of the uniformly doped lithium cobaltate precursor with high element content provided by the invention is 6.02-6.10 g/cm3The unit cell parameter a is between 8.07 and 8.12.
Lithium cobaltate precursors prepared in examples 1 to 3 and comparative example 1 were prepared into lithium batteries, and the prepared lithium batteries were tested under the conditions and results shown in table 2.
Figure BDA0003555408860000121
TABLE 2 Charge-discharge Capacity and 50-cycle Retention ratio of coin cells made from the lithium cobaltate precursors of examples 1-3 and comparative example
As can be seen from table 2, the lithium batteries made from the lithium cobaltate precursors prepared in examples 1 to 3 and comparative example 1 had close charge capacity and discharge capacity, but the lithium batteries made from the lithium cobaltate precursors prepared in examples 1 to 3 had better cycle retention than the lithium batteries made from the prepared lithium cobaltate precursors. This also demonstrates that the lithium cobaltate precursor of the present invention has superior properties.
In addition, research shows that the doping of metal elements (such as aluminum and lanthanum) is influenced by a plurality of factors together, and the change of a single factor cannot show obvious difference. Wherein, the combined action of the stirring frequency, the temperature, the seed crystal granularity, the feeding flow and the PH value has the largest influence on the doping effect, and the washing water temperature and the calcining temperature have smaller influence on the doping effect.
While the invention has been particularly shown and described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (12)

1. A high-element-content uniformly-doped lithium cobaltate precursor is characterized in that: the structural formula of the lithium cobaltate precursor is CoxMyO4Wherein x is more than or equal to 0.95 and less than 1, y is more than 0 and less than or equal to 0.05, M represents doped metal, the crystal system is a cubic crystal system, the space group is F-43M, the unit cell parameter a value of the lithium cobaltate precursor is between 8.07 and 8.12, and the true density is between 6.02g/cm3And 6.10g/cm3In the meantime.
2. The lithium cobaltate precursor according to claim 1, wherein: the doped metal is one or more of Mg, Al, Zr, La, Y, Ni, Mn, Cr, V and Ti.
3. The lithium cobaltate precursor according to claim 1, wherein: the total content of doping metals is between 5000ppm and 15000 ppm.
4. A preparation method of a high-element-content uniformly-doped lithium cobaltate precursor is characterized by comprising the following steps of:
1) adding water into cobalt salt to prepare a cobalt solution, doping metal salt to prepare a metal solution, and preparing alkali required by precipitation into an alkali solution;
2) adding deionized water and an alkali solution into a seed crystal kettle, uniformly stirring, heating to a first temperature to prepare a first base solution, introducing a cobalt solution, the alkali solution and an additive metal solution into a reaction kettle, precipitating at the first temperature, and controlling the pH value to prepare a cobalt carbonate seed crystal;
3) putting part of the cobalt carbonate seed crystals obtained in the step (2) into a long kettle, adding deionized water and an alkali solution, uniformly stirring, heating to a second temperature higher than the first temperature to prepare a second base solution, introducing the cobalt solution, the alkali solution and an additive metal solution into the reaction kettle, precipitating at the second temperature, and controlling the pH value to obtain a cobalt carbonate finished product;
4) after the precipitation is finished, performing solid-liquid separation on the materials in the long kettle, and washing with deionized water to obtain a cobalt carbonate finished product;
5) performing two-stage calcination on cobalt carbonate in a rotary kiln in an oxygen-enriched atmosphere, wherein the first stage is low-temperature calcination, and the second stage is high-temperature calcination to obtain a high-compaction lithium cobaltate precursor, namely the high-tap spheroidal cobaltosic oxide;
6) the crystal system of the prepared cobaltosic oxide is a cubic crystal system, the space group is F-43m, the value of a unit cell parameter is between 8.06 and 8.12, and the true density is 6.02g/cm3And 6.10g/cm3The total content of doped metal is 5000ppm-15000 ppm.
5. The method of claim 4, wherein: the precipitation temperature in the step 2 is 30-40 ℃, and the precipitation temperature in the step 3 is 45-55 ℃.
6. The method of claim 4, wherein: the pH value of the precipitate in the step 2 is 7.0-8.0, and the pH value of the precipitate in the step 3 is 7.0-7.5.
7. The method of claim 4, wherein: the PH value of the first base solution in the step 2 is 7.5-8.5; and the pH value of the second base solution in the step 3 is 7.8-8.3.
8. The method of claim 4, wherein: in the step 2, the alkalinity of the first base solution is 0.25-0.35 mol/L; the alkalinity of the second base solution in the step 3 is 0.2-0.3 mol/L.
9. The method of claim 4, wherein: in the step 2, the stirring speed is 190-230 rpm; the stirring speed in the step 3 is 220-280 rpm.
10. The method of claim 4, wherein: the granularity of the seed crystal of the cobalt carbonate seed crystal prepared in the step 2 is 7-12 mu m; and (4) the granularity of the cobalt carbonate finished product prepared in the step (3) is 15-22 mu m.
11. The method of claim 4, wherein: in the step 3, the flow rate of the cobalt salt is 60-70L/h.
12. The method of claim 4, wherein: in the step 5, the low-temperature calcination temperature of the first section is 250-500 ℃; in the step 5, the temperature of the second-stage high-temperature calcination is 700-850 ℃.
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