CN113247971A - Carbonate precursor and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly discloses a carbonate precursor and a manufacturing method thereof. The carbonate precursor is spindle coral secondary spherical particle formed by piling fibrous primary particles and has a general formula of Mn1‑x‑ yCoxNiyAtCO3And (4) showing. According to the method, carbonate coprecipitation crystallization is adopted, soluble carbonate is used as a precipitant in coprecipitation reaction, the growth of particles is prolonged by low-temperature nucleation and high-temperature growth and concentration equipment, an intermediate with high compactness and high tap density is generated, and the intermediate is subjected to hydrothermal reaction to obtain the spherical carbonate precursor material with low impurity content. Compared with the prior art, the preparation method has simple process and low cost, and the prepared lithium-rich manganese-based carbonate precursorThe content of bulk impurities is low.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a carbonate precursor and a preparation method thereof.
Background
The development of new energy automobiles is a necessary way for China to move from automobile kingdom to automobile kingdom. However, the rapid development of new energy automobiles is restricted by the short endurance mileage and high cost. With the requirement of national subsidy policy on the endurance mileage of new energy vehicles, the industry shuffling is aggravated, and the development of high-performance power batteries becomes the only way for enterprises to survive in fierce competition. At present, the anode material of the power battery commonly used in the world is gradually transited from the original lithium manganate and lithium iron phosphate to ternary materials such as lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate, the energy density is gradually increased, but the safety is still to be improved. The lithium-rich manganese-based material is used as a new-generation lithium battery positive electrode material, uses a large amount of manganese element and LiCoO2Compared with ternary materials, the material has the advantages of low price, good safety and environmental friendliness, can well meet the use requirements of the fields of electric automobiles, energy storage power stations, small electronic products and the like, and is one of the most promising power battery anode materials in the future. However, the lithium-rich manganese-based material still has unsatisfactory points, such as first efficiency, rate capability, cycling stability, and gradual voltage attenuation and impedance increase during cycling, which greatly limits the commercial and industrial application of the lithium-rich manganese-based positive electrode material.
The lithium-rich manganese-based material can be prepared by various methods, but the synthesis method with industrial significance is only limited to synthesis of a precursor by a coprecipitation method and preparation by combining a lithium-mixed high-temperature sintering method. The precursors prepared by the coprecipitation method can be further divided into a hydroxide system and a carbonate system according to different precipitants. According to the hydroxide coprecipitation process of the current ternary precursor material, the electrochemical performance of the prepared lithium-rich manganese-based material is not ideal, and the main reason is that Mn is easy to oxidize to cause the phase splitting of the precursor, and a sintering product is easy to form Li2MnO3And (4) clustering. Using N in the co-precipitation process2Gas shielding and adjusting the complexing agent molar ratio can solve this problem, but the overall cost of production is increased. In addition, in a hydroxide coprecipitation system, the reaction system has high pH value and strong corrosivity, and a large amount of ammonia water is used as a complexing agent, so that a precursor with high compactness and optimal appearance can be prepared, ammonia removal equipment is required for treating ammonia-containing wastewater, and the production cost is increased. Therefore, it is desired to develop a low-cost ammonia precipitation-free process.
At present, lithium-rich manganese-based materials with good electrochemical properties are generally prepared into precursors by adopting a carbonate coprecipitation process, and are also the most technical route for industrial research. However, the carbonate coprecipitation method also has the problems of unstable process, difficult regulation of particle morphology, low tap density and high impurity content, so that the production process of the lithium-rich manganese-based positive electrode material precursor still needs to be deeply researched, and the problem of the consistency of product batches still needs to be improved.
Chinese patent application publication No. CN108557905A discloses a lithium-rich manganese-based material precursor and a preparation method thereof, a lithium-rich manganese-based positive electrode material and a preparation method thereof, and a lithium battery, wherein a leaf-shaped lithium-rich manganese-based material carbonate precursor is generated by controlling mixed metal ion concentration, precipitant concentration, complexing agent concentration, mixing rate, stirring rate, reaction pH and reaction temperature by a carbonate coprecipitation method; the precursor provided by the patent has loose primary fiber stacking, is beneficial to the generation of a foliated shape, has low compactness and low tap density, and is used for preparing the single crystal lithium-rich manganese-based anode material finally after being calcined by lithium mixing. Chinese patent application publication No. CN106797016A discloses a carbonate precursor of lithium nickel manganese cobalt oxide cathode material and a method for producing the same, wherein an ammonia-free system of continuous carbonate coprecipitation is adopted, and a seed crystal is introduced to prepare a carbonate precursor with wider distribution, and the precursor has different D50 and corresponding particle size distribution according to different seed crystal addition amounts. Chinese patent application publication No. CN106795008A discloses a method for preparing impurity-containing cathode material and impurity-containing metal carbonate with preferred morphology, wherein a carbonate precursor is prepared by introducing seed crystals and controlling the molar flow rate ratio CO3/M, wherein the carbonate precursor has a sodium-sulfur molar ratio of 0.4< Na/S <2, 0.4weight% < 2x Na + S <1.6weight%, the content of sodium and sulfur in the precursor is high, and the tap density is low in the embodiment despite the wide particle size distribution of the precursor.
Disclosure of Invention
Aiming at the problems of lower density, high impurity content, high production cost and the like of the carbonate precursor prepared in the prior art, the invention provides the carbonate precursor and the preparation method thereof. The preparation method provided by the invention is simple in process and low in production cost, and the spherical carbonate precursor with good stability and excellent performance can be prepared.
In order to solve the above technical problems, the present invention provides the following technical solutions.
Firstly, the invention provides a carbonate precursor with a chemical general formula of Mn1-x-yCoxNiyAtCO3In the formula, 0<x<0.5，0<y<0.5，0<t<0.05. The primary particles of the carbonate precursor are fibrous, and the primary particles are stacked from the center to the outside in a radiation manner to form spindle coral-shaped secondary spherical particles. The particle size of the carbonate precursor is 3-25 mu m, and the specific surface area is 10-55 m2(ii) a tap density of 1.1 to 2.0g/cm3. The carbonate precursor contains Na and S impurities, and the content and proportion of the impurities reach very low levels, both below 1000 ppm. The impurity content can be even lower based on certain good process designs.
Based on the same inventive concept, the invention also provides a preparation method of the lithium-rich manganese-based carbonate precursor, the method adopts carbonate coprecipitation crystallization, soluble carbonate is used as a precipitator in the coprecipitation reaction, the growth of particles is prolonged by low-temperature nucleation and high-temperature growth and concentration equipment, an intermediate with high compactness and high tap density is generated, and the intermediate is subjected to hydrothermal reaction to obtain the spherical carbonate precursor material with low impurity content.
Specifically, the preparation method of the carbonate precursor comprises the following steps:
s1, preparing a mixed salt solution containing Ni, Co, Mn and M, wherein A is selected from more than one of Mg, B, Al, Cr, Zr, Ti, W and V;
preparing a precipitant solution containing carbonate ions;
preparing a complexing agent solution containing F ions;
s2, carrying out coprecipitation reaction, wherein the coprecipitation reaction comprises two stages of nucleation and growth;
a nucleation stage: simultaneously adding the mixed salt solution, the precipitant solution and the complexing agent solution prepared in the step S1 into a reaction kettle, controlling the reaction temperature to be 25-55 ℃, the reaction pH value to be 10.0-11.0, and the stirring speed to be 300-800rpm/min, and finishing the nucleation reaction when the granularity of the reaction slurry reaches a target value;
and (3) a growth reaction stage: adding the mixed salt solution, the precipitant solution and the complexing agent solution prepared in the step S1 into a reaction kettle at the same time, controlling the reaction temperature to be 35-65 ℃, the reaction pH value to be 9.5-10.5, the stirring speed to be 200 plus one year of 500rpm/min, separating the solid and liquid of the reaction slurry when the granularity of the reaction slurry reaches a target value, adding water to prepare the slurry after the obtained solid phase is aged and washed, transferring the slurry into a hydrothermal reaction kettle, reacting for a certain time at the temperature of 150 plus one year of 250 ℃, and naturally cooling to the room temperature;
and S3, performing solid-liquid separation on the material subjected to the hydrothermal reaction in the step S2, and drying the obtained solid phase to obtain the carbonate precursor.
In the above preparation method, further, in step S1, the total metal ion concentration in the prepared mixed salt solution is 0.5 to 4mol/L, the carbonate ion concentration in the precipitant solution is 0.5 to 4mol/L, and the F ion concentration in the complexing agent solution is 0.1 to 1 mol/L.
Further, the total metal ion concentration in the mixed salt solution is 1-3mol/L, more preferably 2-3 mol/L; the concentration of carbonate ions in the precipitant solution is preferably 1-3mol/L, more preferably 2-3 mol/L; the concentration of F ions in the complexing agent solution is preferably 0.1 to 0.5mol/L, more preferably 0.1 to 0.3 mol/L.
Further, when preparing the mixed salt solution, the nickel salt is selected from one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is selected from one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
The anions of the soluble nickel salt, the soluble cobalt salt and the soluble manganese salt used for preparing the mixed salt solution are preferably the same anions, and in the coprecipitation reaction process, the introduction of impurities can be reduced by adopting the same anion salts, so that the soluble matters left in the mother solution after the coprecipitation reaction are more single, the separation of precipitates is reduced, the recovery of the soluble matters is facilitated, the production cost is reduced, and the environmental protection is facilitated.
Further, when the precipitant is prepared, the precipitant is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Further, when the complexing agent is prepared, the complexing agent is selected from one or more of sodium fluoride, potassium fluoride and ammonium fluoride.
In the above preparation method, further, the reaction kettle is a continuous stirring reaction kettle.
In the above preparation method, further, in the growth stage of step S2, the liquid-solid mass ratio of the reaction system is controlled to be 1 to 19: 1.
in the preparation method, further, in the growth stage of step S2, the liquid-solid ratio of the reaction system is controlled by the concentration device, the slurry overflowed from the reaction kettle is concentrated by the concentration device, and the solid phase after solid-liquid separation is returned to the growth reaction stage, and the cycle is repeated until the target particle size is reached.
In the coprecipitation reaction, soluble carbonate is used as a precipitator, the nucleation reaction stage and the growth reaction stage are independently carried out, key parameters of the reaction, such as stirring speed, pH value, reaction temperature and the like, are adjusted and controlled in different stages, mother liquor produced by the reaction is timely discharged through concentration equipment, the solid content in slurry is adjusted and the like, the precipitate after the reaction is separated and washed is prepared into slurry with certain concentration, the slurry is transferred to a hydrothermal reaction kettle for hydrothermal reaction, and after separation, washing and drying, the spherical lithium-rich manganese-based carbonate precursor which is in fibrous shape and is stacked by radiation from the center to the outside can be obtained.
Compared with the prior art, the preparation method provided by the invention is simple in process and low in cost, and the prepared lithium-rich manganese-based carbonate precursor is low in impurity content.
Drawings
Fig. 1 is an SEM image of the carbonate precursor prepared in example 1.
Fig. 2 is an XRD pattern of the carbonate precursor prepared in 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. Furthermore, those skilled in the art can combine features from the embodiments of this document and from different embodiments accordingly based on the description of this document.
Carbonate precursors can in principle be prepared by reacting MSOs4And Na2CO3And a complexing agent are continuously pumped into the continuous stirring reaction kettle at different flow rates for precipitation reaction to obtain the complex; however, in practical cases, sodium and sulfur are always encapsulated in the particles or embedded in the crystal structure, and the possible reaction equation is:
(1-x)MSO4 +(1-y) Na2CO3 = (M1-xNa2x)[(CO3)1-y(SO4)y] +(1-x-y) Na2SO4wherein x and y are less than 0.01; the impurity content has a significant influence on the performance of the cathode material, and the cathode material with excellent performance can be obtained only if the impurity content needs to be controlled at a lower level.
In general, Na/S =2x/y in the carbonate precursor may characterize the presence of impurities. The Na/S content of the carbonate precursor is controlled within the range of 0.5-10. When the Na/S is 0.5-2, indicating that the sodium sulfate is wrapped in the particles or adsorbed on the surfaces of the particles; when Na/S > 2, it means that not only sodium sulfate is encapsulated in the interior of the particles, but also sodium is incorporated into the crystal lattice. According to the technical scheme provided by the invention, the content of Na and S meets the formula: 2 Na + S <0.5 weight%.
The specific surface area of the obtained carbonate precursor was measured by standard BET method on a 3H-2000BET type a specific surface test system; particle size was tested on a Malvern Mastersizer 2000; testing components and impurities on an ICP-AES system of PE-8000; tap density was tested on a Baiter BT-301.
The method comprises the steps of simultaneously pumping mixed metal ion solution, precipitator solution and complexing agent solution into a continuous stirring reaction kettle through a peristaltic pump, controlling the flow rate ratio of the precipitator solution to the mixed metal ion solution, ensuring the pH value of a reaction system, carrying out nucleation reaction and growth reaction in stages, removing mother liquor generated in the reaction kettle through a thickening device communicated with the reaction kettle, enabling the total feed flow and the mother liquor discharge flow to be equal so as to keep the liquid level in the thickening device unchanged, intercepting all generated materials in a synthesis kettle, gradually increasing the concentration of the whole slurry, and continuously growing particles until the particles grow to a target value; then separating the materials in the reaction kettle, washing and removing impurities, adding water, mixing the slurry, pumping the slurry into a hydrothermal reaction kettle, and maintaining a certain temperature and time for hydrothermal reaction; and then, separating, washing and drying the reacted materials to obtain the fibrous primary particles with low impurity content, and stacking the fibrous primary particles into the carbonate precursor in the form of spindle coral-shaped secondary spherical particles.
In the preparation method of the carbonate precursor provided by the invention, the retention time of the materials in the reaction kettle is determined by the integral slurry concentration when the particle size grows to a target value and the particle size and the number of crystal nuclei at the end of the nucleation reaction stage. Assuming that the mass of the material fed into the reaction kettle per hour is M, the slurry concentration at the end of the nucleation reaction is M1 and the particle size is D1, and the slurry concentration at the time of growth to the target particle size is M2 and the particle size is D2, the residence time T =100 (M2-M1)/M (h). The residence time can therefore be varied by varying the pump speed, i.e. the mass or flow rate supplied per hour, and the number of nuclei. The flow rate ratio of the precipitant solution to the mixed metal ion solution in the nucleation reaction stage is far greater than 1, the temperature is controlled to be 25-55 ℃, and the pH is controlled to be 10.00-11.00; the flow rate ratio of the precipitator solution and the mixed metal ion solution in the growth reaction stage is more than 1, preferably more than 1 and less than 1.5, the temperature is controlled to be 35-65 ℃, and the pH is controlled to be 9.50-10.50. In the nucleation stage, the ratio of the amounts of the mixed salt solution and the precipitant pumped into the reactor is controlled to be much greater than 1, preferably greater than > 3. As the reaction proceeds, the pH in the reaction kettle slowly decreases as the reaction proceeds. And then, adjusting parameters such as flow ratio, temperature, pH and the like of the precipitant and the mixed metal solution to carry out growth reaction, wherein CO3/M is preferably more than 1, and is particularly preferably controlled within the range of 0.9-1.2. After the precipitation reaction is finished, separating, washing and mixing the materials, pumping the materials into a hydrothermal reaction kettle, reacting for 2-6 h at the temperature of 150-250 ℃, preferably 180-220 ℃, naturally cooling to room temperature, washing and drying to obtain the carbonate precursor with low impurity sodium and sulfur content and piled fibrous primary particles into spindle coral secondary spherical particles.
For a better understanding of the present invention, reference will now be made in detail to specific embodiments thereof.
Example 1
Preparation of a feed solution: manganese sulfate, cobalt sulfate, nickel sulfate and magnesium sulfate are mixed according to a stoichiometric molar ratio Mn: co: ni: a =0.70:0.15:0.15:0.01 was dissolved in deionized water to prepare a mixed metal ion solution having a total metal ion concentration of 2 mol/L. Sodium carbonate is dissolved in deionized water to prepare a 2mol/L precipitator solution. Sodium fluoride is dissolved in deionized water to prepare 0.2mol/L complexing agent solution.
② coprecipitation reaction: in the nucleation reaction stage, regulating the flow rates of a sodium carbonate solution and a mixed metal ion solution according to the mole ratio of carbonate ions to total metal ions =3:1, controlling the concentration of a complexing agent in the total feeding solution at 0.01mol/L, and simultaneously pumping the solution into a 100L continuous stirring reaction kettle, wherein 50L of the sodium carbonate solution is filled in the reaction kettle as a base solution; controlling the nucleation reaction temperature to be 30 ℃, stirring the reaction product at the rotating speed of 600rpm, slowly reducing the pH value along with the progress of the precipitation reaction after feeding for a period of time, changing the pH value between 11.00 and 10.50, monitoring the particle size of the slurry in the reaction kettle in real time by a particle size analyzer until the particle size distribution in a particle size diagram is normal, and finishing the nucleation reaction stage, wherein the particle size is less than 2 microns. And in the grain size growth reaction stage, the mole ratio of carbonate ions to total metal ions in the previous stage is adjusted to be 1.3:1, the stirring speed is 500rpm, the reaction temperature is 45 ℃, and the pH value is slowly reduced along with the progress of the precipitation reaction and is changed between 10.50 and 9.80. In the reaction process, the overflow port of the reaction kettle is closed, the mother liquor is continuously discharged from the reaction kettle through a thickening device (a settling tank), and the reaction slurry is intercepted in the reaction kettle, so that no material is discharged until the reaction slurry reaches the target granularity. The particle size distribution of the final material is determined by the particle size distribution of the nucleation stage.
Thirdly, separating, aging and washing the slurry after the growth reaction, adding water for size mixing, transferring the slurry into a hydrothermal reaction kettle, controlling the hydrothermal reaction temperature to be 150 ℃, 180 ℃ and 200 ℃ respectively, and carrying out hydrothermal reaction for 2 hours.
Comparative example 1
Comparative example 1 compared to example 1, step three was omitted.
TD and D of carbonate precursor prepared in example 1 and comparative example 1 were detected and analyzed50BET, Na and S contents, the results are shown in table 1.
TABLE 1 physicochemical indices of carbonate precursors
By comparing the physical and chemical indexes of the carbonates prepared in example 1 and comparative example 1, it can be found that the hydrothermal reaction is important for reducing the Na content in the carbonate precursor.
Fig. 1 is an SEM image of a carbonate precursor prepared in example 1 at a hydrothermal reaction temperature of 180 ℃, and it can be seen from the figure that secondary particles of the carbonate precursor are spindle coral-shaped and are stacked in a state where fibrous primary particles are irradiated.
Fig. 2 is an XRD pattern of the carbonate precursor prepared in example 1 at a hydrothermal reaction temperature of 180 ℃, and it can be seen that the prepared precursor is a pure phase and has high crystallinity.
Example 2:
preparation of a feed solution: manganese sulfate, cobalt sulfate, nickel sulfate and aluminum sulfate are mixed according to the stoichiometric ratio of Mn: co: ni: a =0.60:0.20:0.20:0.01 was dissolved in deionized water to prepare a mixed metal ion solution having a total metal ion concentration of 2 mol/L. Sodium carbonate is dissolved in deionized water to prepare a 2mol/L precipitator solution. Sodium fluoride is dissolved in deionized water to prepare 0.2mol/L complexing agent solution.
② coprecipitation reaction: in the nucleation reaction stage, the pumping flow rate of the materials is adjusted according to the mole ratio of carbonate ions to total metal ions of 5:1 of sodium carbonate solution and mixed metal ion solution, the concentration of the complexing agent in the total feeding solution is controlled to be 0.012mol/L, and the complexing agent is pumped into a 100L continuous stirring reaction kettle which is filled with 50L of sodium carbonate solution as a base solution; the nucleation reaction temperature is controlled to be 40 ℃, the stirring speed is 800rpm, after the material is fed for a period of time, the pH value is slowly reduced and is changed between 11.00 and 10.80 along with the progress of the precipitation reaction, the particle size of the slurry in the reaction kettle is monitored in real time by a particle size analyzer until the particle size distribution in a particle size diagram is normal, the nucleation reaction stage is completed, and the particle size is less than 2 microns at the moment. And in the grain size growth reaction stage, the mole ratio of carbonate ions to total metal ions in the previous stage is adjusted to be 1.2:1, the stirring speed is 600rpm, the reaction temperature is 55 ℃, and the pH value is slowly reduced along with the progress of the precipitation reaction and is changed between 10.80 and 10.20. In the reaction process, the overflow port of the reaction kettle is closed, the mother liquor is continuously discharged from the reaction kettle through a thickening device (a settling tank), and the reaction slurry is intercepted in the reaction kettle, so that no material is discharged until the reaction slurry reaches the target granularity.
Thirdly, separating, aging and washing the slurry after the growth reaction, adding water for size mixing, transferring the slurry into a hydrothermal reaction kettle, controlling the hydrothermal reaction temperature to be 180 ℃, 200 ℃ and 220 ℃ respectively, and carrying out hydrothermal reaction for 2 hours.
Comparative example 2-1:
comparative example 2-1 is different from example 2 in that there is no process of step (c).
Comparative examples 2 to 2:
the hydrothermal reaction temperature of step (c) of comparative example 2-2 was 200 ℃, which is different from that of example 2 in that: in the growth reaction stage, the overflow port is opened, the slurry is retained in the reaction kettle without using a thickening device (a settling tank), the retention time of the particles is rapidly reduced, and the growth is faster.
Comparative examples 2 to 3:
the hydrothermal reaction temperature of step (c) of comparative example 2-3 was 200 ℃, which is different from that of example 2 in that: in the growth reaction stage, a sodium fluoride complexing agent is not pumped into the reaction kettle, and in the precipitation reaction process, free manganese ions in the reaction kettle are not complexed by fluorine ions in advance, but are combined with cobalt ions and nickel ions together with carbonate ions to form a precipitate, so that the growth is fast.
Detection analysis TD and D of carbonate precursor prepared in example 2 and comparative example 250BET, Na and S contents, the results are shown in table 2.
TABLE 2 physicochemical indices of carbonates
By comparing the example 2 with the comparative examples 2-1, 2-2 and 2-3, it is obvious that the technical scheme provided by the invention has particularly important significance for improving the tap density of the carbonate precursor and reducing the Na and S contents.
Example 3:
preparation of a feed solution: manganese sulfate, cobalt sulfate, nickel sulfate and magnesium sulfate are mixed according to the stoichiometric ratio Mn: co: ni: a =0.50:0.20:0.30:0.01 was dissolved in deionized water to prepare a mixed metal ion solution having a total metal ion concentration of 2 mol/L. Sodium carbonate is dissolved in deionized water to prepare a 2mol/L precipitator solution. Sodium fluoride is dissolved in deionized water to prepare 0.2mol/L complexing agent solution.
② coprecipitation reaction: in the nucleation reaction stage, the pumping flow rate of the materials is adjusted according to the mole ratio of carbonate ions to total metal ions of 3:1 of sodium carbonate solution and mixed metal ion solution, the concentration of the complexing agent in the total feeding solution is controlled to be 0.01mol/L, and the complexing agent is pumped into a 100L continuous stirring reaction kettle which is filled with 50L of sodium carbonate solution as a base solution; controlling the nucleation reaction temperature to be 45 ℃, stirring the reaction product at a rotating speed of 700rpm, slowly reducing the pH value along with the progress of the precipitation reaction after feeding for a period of time, changing the pH value between 10.80 and 10.00, monitoring the particle size of the slurry in the reaction kettle in real time by a particle size analyzer until the particle size distribution in a particle size diagram is normal, and finishing the nucleation reaction stage, wherein the particle size is less than 2 microns. And in the grain size growth reaction stage, the mole ratio of carbonate ions to total metal ions in the previous stage is adjusted to be 1.1:1, the stirring speed is 600rpm, the reaction temperature is 65 ℃, and the pH value is slowly reduced along with the progress of the precipitation reaction and is changed between 10.00 and 9.50. In the reaction process, the overflow port of the reaction kettle is closed, the mother liquor is continuously discharged from the reaction kettle through a thickening device (a settling tank), and the reaction slurry is intercepted in the reaction kettle, so that no material is discharged until the reaction slurry reaches the target granularity. The particle size distribution of the final material is determined by the particle size distribution of the nucleation stage.
Thirdly, separating, aging and washing the slurry after the growth reaction, adding water for size mixing, transferring the slurry into a hydrothermal reaction kettle, controlling the hydrothermal reaction temperature to be 150 ℃, 180 ℃ and 200 ℃ respectively, and carrying out hydrothermal reaction for 2 hours.
Comparative example 3:
comparative example 3 differs from example 3 in that: and (4) directly obtaining a carbonate precursor without the step III.
TD and D of carbonate precursor prepared in example 3 and comparative example 3 were detected and analyzed50BET, Na and S contents, the results are shown in table 3 below.
TABLE 3 carbonate physicochemical indices
The importance of hydrothermal reaction on the reduction of Na content in the carbonate precursor is further illustrated from the physicochemical index data in table 3.
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 (10)
1. A carbonate precursor, which is characterized in that the chemical general formula is Mn1-x-yCoxNiyAtCO3In the formula, 0<x<0.5，0<y<0.5，0<t<0.05; the primary particles are fibrous, and the primary particles are radiated and accumulated from the center to the outside to form spindle coral-shaped secondary spherical particles; the particle size of the carbonate precursor is 3-25 mu m, and the specific surface area is 10-55 m2(ii) a tap density of 1.1 to 2.0g/cm3(ii) a The content of the carbonate precursors Na and S is below 1000 ppm.
2. A method for preparing a carbonate precursor according to claim 1, comprising the steps of:
s1, preparing a mixed salt solution containing Ni, Co, Mn and M, wherein A is selected from more than one of Mg, B, Al, Cr, Zr, Ti, W and V;
preparing a precipitant solution containing carbonate ions;
preparing a complexing agent solution containing F ions;
s2, carrying out coprecipitation reaction, wherein the coprecipitation reaction comprises two stages of nucleation and growth;
a nucleation stage: simultaneously adding the mixed salt solution, the precipitant solution and the complexing agent solution prepared in the step S1 into a reaction kettle, controlling the reaction temperature to be 25-55 ℃, the reaction pH value to be 10.0-11.0, and the stirring speed to be 300-800rpm/min, and finishing the nucleation reaction when the granularity of the reaction slurry reaches a target value;
and (3) a growth reaction stage: adding the mixed salt solution, the precipitant solution and the complexing agent solution prepared in the step S1 into a reaction kettle at the same time, controlling the reaction temperature to be 35-65 ℃, the reaction pH value to be 9.5-10.5, the stirring speed to be 200 plus one year of 500rpm/min, separating the solid and liquid of the reaction slurry when the granularity of the reaction slurry reaches a target value, adding water to prepare the slurry after the obtained solid phase is aged and washed, transferring the slurry into a hydrothermal reaction kettle, reacting for a certain time at the temperature of 150 plus one year of 250 ℃, and naturally cooling to the room temperature;
and S3, performing solid-liquid separation on the material subjected to the hydrothermal reaction in the step S2, and drying the obtained solid phase to obtain the carbonate precursor.
3. The method of claim 2, wherein in step S1, the total metal ion concentration in the prepared mixed salt solution is 0.5 to 4mol/L, the carbonate ion concentration in the precipitant solution is 0.5 to 4mol/L, and the F ion concentration in the complexing agent solution is 0.1 to 1 mol/L.
4. The method according to claim 2 or 3, wherein in the step S1, when the mixed salt solution is prepared, the nickel salt is selected from one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate; the cobalt salt is selected from one or more of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt is selected from one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
5. The method according to claim 4, wherein the mixed salt solution is prepared by using the same anion as the anion of the nickel salt, cobalt salt or manganese salt.
6. The method according to claim 2, wherein in step S1, when preparing the precipitant, the precipitant is selected from one or more of sodium carbonate, sodium bicarbonate, potassium carbonate, and potassium bicarbonate; when the complexing agent is prepared, the complexing agent is selected from one or more of sodium fluoride, potassium fluoride and ammonium fluoride.
7. The method according to claim 2, wherein the reaction vessel in step S2 is a continuous stirring reaction vessel.
8. The production method according to claim 2, wherein in the growth stage of step S2, the liquid-solid mass ratio of the reaction system is controlled to be 1 to 19: 1.
9. the production method according to claim 8, wherein in the growth stage of step S2, the liquid-solid ratio of the reaction system is controlled by a concentration device.
10. The preparation method according to claim 9, wherein the slurry overflowed from the reaction vessel is concentrated by a concentration device, and the solid phase after solid-liquid separation is returned to the growth reaction stage, and is circulated until the target particle size is reached.
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