CN111276688B - Cerium-zirconium co-doped porous structure cathode material and preparation method thereof - Google Patents
Cerium-zirconium co-doped porous structure cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a cerium-zirconium co-doped porous structure anode material and a preparation method thereof. The method comprises the following steps: (1) preparing a ternary solution, a cerium-zirconium mixed salt solution, a precipitator solution and a complexing agent solution for later use; (2) preparing base solution and stirring; (3) injecting a ternary solution, a mixed solution of cerium salt and zirconium salt, a precipitator solution and a complexing agent solution into a base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size; (4) centrifugally washing, drying, screening and deironing the reacted slurry to obtain a precursor; (5) and mixing the precursor with a lithium source, and sintering to obtain the cathode material. The method utilizes liquid phase doping to dope the blended cerium-zirconium salt solution into the ternary solution, so that the doping elements are uniformly distributed, and the battery cycle performance of the material is improved by utilizing the synergistic effect of the doping elements; the anode material with a pore structure, high purity and good performance is prepared by process control at different reaction stages.
Description
Technical Field
The invention belongs to the field of electrode materials and the field of electrochemical energy storage, and particularly relates to a cerium-zirconium co-doped porous structure anode material and a preparation method thereof.
Background
The anode material is the most important component of the lithium ion battery, and is concerned with the performance parameters of the lithium ion battery, such as capacity, multiplying power, safety performance, cycle times, service life and the like, and the product price.
Currently, a positive electrode material having a pore structure is increasingly focused and studied. The porous anode material has the following advantages: on one hand, the porous material can store more electrolyte to improve the cycle performance in the charge and discharge process; on the other hand, the porous structure can provide more storage and accommodation spaces under the overcharge condition of the lithium ion battery, and the safety performance of the lithium ion battery is improved.
The pursuit of high capacity leads the ternary material to develop towards high nickel, but the problems of cycle performance, safety and the like of the high nickel material are prominent, and the high nickel material needs to be modified by doping, coating and the like. At present, most of the doping modes in industrial production are solid-phase methods, namely doping is carried out in the process of burning the anode material.
In the document "research on preparation of porous nickel-cobalt-aluminum ternary cathode material", a method for preparing a porous cathode material is reported, in which a carbon nanotube dispersion liquid is added in the preparation process of a precursor, and carbon nanotubes are removed due to high temperature in the later sintering process of the cathode material, thereby leaving holes in the cathode material.
CN 109616664 a discloses a nickel-cobalt-manganese precursor, a method for preparing a nickel-cobalt-manganese ternary material, and a lithium ion battery, wherein the preparation method starts with the preparation of a high-nickel ternary material precursor, and adopts organic polymer particles as a pore-forming agent and a substance obtained by carbonizing the organic polymer particles in lithiation sintering as a reducing agent to prepare a high-nickel ternary positive electrode material in which inner voids exist in secondary particles and primary particles contain a transition metal ion gradient layer.
The pore-forming method in the prior art is mostly realized by adding pore-forming agent or surfactant, i.e. other substances are required to be introduced. In actual industrial production, the requirement of customers on impurities of products is extremely strict, and even carbon has extremely strict index requirements. Meanwhile, the addition of other substances increases the production process and auxiliary materials, and the manufacturing cost of the product is further increased.
The sintering temperature of the high nickel material is lower, the element distribution is difficult to be uniform at low temperature of solid phase doping, and the battery performance of the material can be reduced. In addition, the selection of the doping element also affects the battery performance, and the problem of how to improve the cycle performance of the battery by the doping element under the condition of high nickel needs to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a cerium-zirconium co-doped porous structure cathode material and a preparation method thereof.
The invention utilizes liquid phase doping to dope the blended cerium-zirconium salt solution into the ternary solution, so that the doping elements are uniformly distributed, and Zr is added4+The layered structure of the anode material can be stabilized, the mixed discharge of cations is reduced, and the cycle performance is improved; and Ce4+The electronic conductivity and the diffusion rate of lithium ions can be improved, so that the discharge capacity is improved; the synergistic effect of cerium and zirconium can simultaneously improve the capacity and the cycle performance of the material, and the battery performance can be improved from multiple aspects compared with the battery performance which is doped by using a single element. Further, the pH value of the reaction system is adjusted through adding of a precipitator and controlling of flow rate in different reaction stages, and stirring rotation speed is adjusted in different stages, so that the anode material with a pore structure is prepared, and a pore-forming agent or a surfactant is not required to be added in the preparation process. The pH value of the base solution is lower than that of a product with the same normal particle size, the ammonia concentration of the supernatant is higher, the particle size of the starting machine can be increased, the pH value of the reaction in the first stage is also lower, the ammonia concentration is higher, the growth speed can be accelerated, and the particle size can reach more than 90% of the target particle size in a short time. And in the second stage, the reaction pH and the stirring speed are further reduced, the ammonia concentration is improved, the growth speed is kept not to be slowed down under the condition that the solid content is increased all the time, the total reaction time is shortened, the inside and the outside of the precursor are kept loose as well, and primary particles are fine due to the high growth speed. When the anode is sintered, the primary particles of the precursor are fine and uniform and are agglomerated and loosened, so that gaps formed inside are uniform, and the purpose of sintering the anode can be achievedThe effect of adding pore-forming agent. The prepared anode material has high purity, uniform element doping and good battery cycle performance.
The technical scheme provided by the invention is as follows:
a preparation method of a cerium-zirconium co-doped porous structure cathode material comprises the following steps:
(1) preparing a ternary solution, a cerium-zirconium mixed salt solution, a precipitator solution and a complexing agent solution for later use;
(2) preparing base solution and stirring;
(3) injecting a ternary solution, a mixed solution of cerium salt and zirconium salt, a precipitator solution and a complexing agent solution into a base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size;
(4) centrifugally washing, drying, screening and deironing the reacted slurry to obtain a precursor;
(5) and mixing the precursor with a lithium source, and sintering to obtain the cathode material.
Further, the ternary solution is a sulfate solution containing Ni, Co and Mn; the concentration of total metal ions in the solution is 1-3 mol/L; the precipitant solution is 20-32% of industrial liquid alkali; the complexing agent solution is ammonia water, and the mass concentration of the complexing agent solution is 15-20%.
Further, the cerium-zirconium blended salt is selected from sulfate, nitrate or chloride of the cerium-zirconium blended salt, and the molar ratio of cerium to zirconium is 0.5-2: 1. Preferably, the concentration of the cerium-zirconium mixed salt is 0.02-0.05 mol/L.
Further, the preparation method of the base solution in the step (2) is as follows: adding a complexing agent solution into pure water in the atmosphere of nitrogen, and adjusting the pH value by using a precipitator solution to obtain the water-soluble organic silicon dioxide;
wherein the pH value of the base solution is controlled to be 11-12, the ammonia concentration is 6-10g/L, the temperature is 40-80 ℃, and the stirring speed is 200-600 rpm.
Further, the flow rate of the ternary solution in the step (3) is 600L/h, the flow rate of the mixed solution of cerium salt and zirconium salt is 30-200L/h, the flow rate of the precipitant solution is 30-200L/h, and the flow rate of the complexing agent solution is 10-100L/h.
Further, the reaction time of the reaction stage I in the step (3) is 10-30 h, the pH is controlled to be 11.2-11.8, and the ammonia concentration is controlled to be 6-10 g/L; the stirring speed is controlled at 200-600 rpm; the adjustment is made by fine-tuning the flow rates of the precipitant solution and the complexing agent solution to maintain the pH and ammonia concentration within the ranges.
Further, the pH value of the reaction stage II in the step (3) is controlled to be 10.6-11.2, and the ammonia concentration is controlled to be 8-15 g/L; the stirring speed is controlled at 150-550 rpm; the adjustment mode is to adjust the precipitant solution to reduce the pH value, increase the flow of the complexing agent and increase the ammonia concentration.
Further, the pH and the stirring rotation speed of the reaction stage II in the step (3) are lower than those of the reaction stage I; the supernatant ammonia concentration of reaction stage II was 2-5g/L higher than that of stage I.
Further, the target particle size D50 in the step (3) is 3-5 μm.
The invention also aims to provide the cerium-zirconium co-doped porous structure cathode material prepared by the method.
The invention has the beneficial effects that:
1. and liquid phase doping is adopted, so that the distribution of doping elements is more uniform, the formation of effective synergistic effect between cerium and zirconium is facilitated, and the cycle performance of the battery is improved.
2. Pore-forming agents or surfactants are not needed, the pH of the reaction system is adjusted only in different reaction stages through the addition of a precipitator and the control of flow rate, and precursors with fine and uniform inner and outer primary particles are prepared by aiming at the adjustment of stirring rotation speed and ammonia concentration in different stages, and a porous structure is formed in the anode material after sintering.
3. Under the condition of not increasing the production cost, the structure of the precursor and the anode material thereof is changed, the rate capability of the anode material is improved, the production cost is not increased, the cost control is facilitated, and the method can be used for industrial mass production;
4. the ratio of the diffraction intensity of the crystal planes (001) and (101) of the XRD of the product is controlled to be less than 1, so that lithium ion migration is facilitated, and the performance of the battery material is improved.
5. The prepared anode material is beneficial to the infiltration of electrolyte, shortens the diffusion path of lithium ions and improves the rate capability of the material.
6. Provides a new idea for preparing the cerium-zirconium co-doped porous structure anode material with the internal porous structure, and has a wide application prospect.
Drawings
Fig. 1 is an SEM image and a doping element distribution diagram of the precursor and the cathode material prepared in example 1; wherein, fig. 1(a) is a precursor, fig. 1(b) is a positive electrode material, fig. 1(c) is a distribution diagram of zirconium element in the precursor, and fig. 1(d) is a distribution diagram of cerium element in the precursor;
fig. 2 is an SEM image and a doping element distribution diagram of the precursor and the cathode material prepared in the comparative example; wherein, fig. 2(a) is a precursor, fig. 2(b) is a positive electrode material, fig. 2(c) is a distribution diagram of zirconium element in the precursor, and fig. 2(d) is a distribution diagram of cerium element in the precursor;
FIG. 3 is an XRD pattern of the precursor prepared in example 1;
fig. 4 is an XRD pattern of the precursor prepared in the comparative example.
Detailed Description
The invention will be further illustrated with reference to specific examples, to which the present invention is not at all restricted.
A preparation method of a cerium-zirconium co-doped porous structure cathode material comprises the following steps:
(1) preparing a ternary solution, a cerium-zirconium mixed salt solution, a precipitator solution and a complexing agent solution for later use;
(2) preparing base solution and stirring;
(3) injecting a ternary solution, a mixed solution of cerium salt and zirconium salt, a precipitator solution and a complexing agent solution into a base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size;
(4) centrifugally washing, drying, screening and deironing the reacted slurry to obtain a precursor;
(5) mixing the precursor with a lithium source, and sintering to obtain a positive electrode material; preferably, the cerium-zirconium co-doped ternary precursor is mixed with a lithium source, and the mixture is sintered for 10 to 20 hours at the temperature of 700-1000 ℃ in the air or oxygen atmosphere to obtain the cerium-zirconium co-doped porous structure cathode material.
Further, the ternary solution is a sulfate solution containing Ni, Co and Mn; the concentration of total metal ions in the solution is 1-3 mol/L; the precipitant solution is 20-32% of industrial liquid alkali; the complexing agent solution is ammonia water, and the mass concentration of the complexing agent solution is 15-20%.
Further, the cerium-zirconium blended salt is selected from sulfate, nitrate or chloride of the cerium-zirconium blended salt, and the molar ratio of cerium to zirconium is 0.5-2: 1.
Further, the preparation method of the base solution in the step (2) is as follows: adding a complexing agent solution into pure water in the atmosphere of nitrogen, and adjusting the pH value by using a precipitator solution to obtain the water-soluble organic silicon dioxide;
wherein the pH value of the base solution is controlled to be 11-12, the ammonia concentration is 6-10g/L, the temperature is 40-80 ℃, and the stirring speed is 200-600 rpm.
Further, the flow rate of the ternary solution in the step (3) is 600L/h, the flow rate of the mixed solution of cerium salt and zirconium salt is 30-200L/h, the flow rate of the precipitant solution is 30-200L/h, and the flow rate of the complexing agent solution is 10-100L/h.
Further, the reaction time of the reaction stage I in the step (3) is 10-30 h, the pH is controlled to be 11.2-11.8, and the ammonia concentration is controlled to be 6-10 g/L; the stirring speed is controlled at 200-600 rpm; the adjustment is made by fine-tuning the flow rates of the precipitant solution and the complexing agent solution to maintain the pH and ammonia concentration within the ranges.
Further, in the step (3), the pH value of the reaction stage II is controlled to be 10.6-11.2, and the ammonia concentration is controlled to be 8-15 g/L; the stirring speed is controlled at 150-550 rpm; the adjustment mode is to adjust the precipitant solution to reduce the pH value, increase the flow of the complexing agent and increase the ammonia concentration.
Further, the pH and the stirring rotation speed of the reaction stage II in the step (3) are lower than those of the reaction stage I; the ammonia concentration of the supernatant in the reaction stage II is improved by about 2-5g/L compared with that in the stage I.
Further, the target particle size D50 in the step (3) is 3-5 μm.
Example 1
Preparation of cerium-zirconium co-doped NCM811 porous cathode material
The method comprises the following steps:
step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into an aqueous solution A with a total metal concentration of 2mol/L according to a metal molar ratio of 8:1:1, preparing cerium sulfate and zirconium sulfate into an aqueous solution B with a total metal concentration of 0.05mol/L according to a metal molar ratio of 1:2, and adopting 32% industrial liquid alkali as a precipitator C and 17% ammonia water as a complexing agent D.
Step 2, adding 5000L of pure water into the reaction kettle and introducing N2As a protective gas, the ammonia concentration of the base solution was adjusted to 10g/L with the solution D, and the pH of the base solution was adjusted to 11.9-12.0 with the solution C. The temperature was set at 60 ℃ and the stirring speed was set at 400 rpm.
And 3, simultaneously and respectively adding the solution A, the solution B, the solution C and the solution D into a reaction kettle at the speed of 600L/h, 100L/h, 240L/h and 40L/h to carry out the reaction of the stage I and the stage II:
stage I: the pH value of a reaction system is controlled to be 11.2-11.4 and the ammonia concentration is controlled to be 6-7g/L by fine adjustment of the flow rates of liquid caustic soda and ammonia water, and the reaction is carried out for 16 hours;
stage II: adjusting the flow rate of liquid caustic soda to 235L/h, reducing the pH value to 10.8-11.0, adjusting the flow rate of ammonia water to 55L/h, increasing the ammonia concentration to 8-9g/L, adjusting the stirring speed to 350rpm, continuously reacting until D50 reaches 4.0um, and stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening, removing iron, and packaging to obtain the cerium-zirconium co-doped NCM811 ternary precursor.
And 5, mixing the precursor with LiOH monohydrate according to a lithiation ratio of 1.02, and sintering at 800 ℃ for 15 hours in an oxygen atmosphere to obtain the cerium-zirconium co-doped NCM811 porous anode material.
Example 2
Preparation of cerium-zirconium co-doped NCM880606 porous cathode material
The method comprises the following steps:
step 1, preparing aqueous solution A with the total metal concentration of 2mol/L from nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of 88:6:6, preparing aqueous solution B with the total metal concentration of 0.02mol/L from cerium sulfate and zirconium sulfate according to the metal molar ratio of 1:1, and adopting 32% industrial liquid alkali as precipitator C and 17% ammonia water as complexing agent D.
Step 2, adding into a reaction kettleAdding 5000L of pure water and introducing N2As a protective gas, the ammonia concentration of the base solution was adjusted to 7.5g/L with solution D, and the pH of the base solution was adjusted to 11.8 to 11.9 with solution C. The temperature was set at 65 ℃ and the stirring speed was set at 380 rpm.
And 3, simultaneously and respectively adding the solution A, the solution B, the solution C and the solution D into a reaction kettle at the speed of 400L/h, 100L/h, 160L/h and 35L/h to carry out the reaction of the stage I and the stage II:
stage I: the pH value of a reaction system is controlled to be 11.4-11.6 and the ammonia concentration is controlled to be 7-8g/L by fine adjustment of the flow rates of liquid caustic soda and ammonia water, and the reaction is carried out for 20 hours;
stage II: adjusting the flow rate of the liquid caustic soda to 158L/h, reducing the pH to 10.6-10.8, adjusting the flow rate of the ammonia water to 45L/h, controlling the ammonia concentration to 9-10g/L, adjusting the stirring speed to 320rpm, continuously reacting until the D50 reaches 5.0um, and stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening, removing iron, packaging, and obtaining a cerium-zirconium co-doped NCM880606 ternary precursor finished product.
And 5, mixing the precursor with LiOH monohydrate according to the lithiation proportion of 1.05, and sintering for 16 hours at 780 ℃ in an oxygen atmosphere to obtain the cerium-zirconium co-doped NCM880606 porous anode material.
Example 3
Cerium-zirconium co-doped NCM960202 porous cathode material
The method comprises the following steps:
step 1, preparing aqueous solution A with the total metal concentration of 2mol/L from nickel sulfate, cobalt sulfate and manganese sulfate according to the metal molar ratio of 96:2:2, preparing aqueous solution B with the total metal concentration of 0.02mol/L from cerium sulfate and zirconium sulfate according to the metal molar ratio of 2:1, and adopting 32% industrial liquid alkali as precipitator C and 17% ammonia water as complexing agent D.
Step 2, adding 5000L of pure water into the reaction kettle and introducing N2As a protective gas, the ammonia concentration of the base solution was adjusted to 8.5g/L with solution D, and the pH of the base solution was adjusted to 11.6-11.7 with solution C. The temperature was set at 68 ℃ and the stirring speed was set at 420 rpm.
And 3, simultaneously and respectively adding the solution A, the solution B, the solution C and the solution D into a reaction kettle at the speed of 400L/h, 100L/h, 160L/h and 40L/h to carry out the reaction of the stage I and the stage II:
stage I: controlling the pH value of a reaction system to be 11.2-11.4 and the ammonia concentration to be 8-9g/L by finely adjusting the flow rates of liquid caustic soda and ammonia water, and reacting for 30 hours;
stage II: adjusting the flow rate of the liquid caustic soda to 155L/h, adjusting the flow rate of ammonia water to 52L/h when the pH is reduced to 10.7-10.9, controlling the concentration of ammonia to 10-11g/L, adjusting the stirring speed to 360rpm, and continuing to react until D50 reaches 4.0um, and then stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening, removing iron, and packaging to obtain the cerium-zirconium co-doped NCM960202 ternary precursor.
And 5, mixing the precursor with LiOH monohydrate according to a lithiation ratio of 1.08, and sintering at 720 ℃ for 18 hours in an oxygen atmosphere to obtain the cerium-zirconium co-doped NCM960202 porous anode material.
Comparative example
Preparation of solid-phase doped cerium-zirconium co-doped NCM811 cathode material
Step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into an aqueous solution A with a total metal concentration of 2mol/L according to a metal molar ratio of 8:1:1, and adopting 32% of industrial liquid alkali as a precipitator B and 17% of ammonia water as a complexing agent C.
Step 2, adding 5000L of pure water into the reaction kettle and introducing N2As a protective gas, the ammonia concentration of the base solution was adjusted to 4g/L with the solution C, and the pH of the base solution was adjusted to 12.0 to 1.2.1 with the solution B. The temperature was set at 60 ℃ and the stirring speed was set at 450 rpm.
And 3, simultaneously adding the solution A, the solution B and the solution C into the reaction kettle at the speed of 400L/h, 160L/h and 30L/h respectively, and finely adjusting the flow rates of the solution B and the solution C to keep the reaction pH at 11.6-11.8 and the ammonia concentration at 4-5 g/L.
And 4, stopping feeding after D50 reaches 4um, performing centrifugal washing, drying, screening, deironing and packaging to obtain the cerium-zirconium co-doped NCM811 ternary precursor.
And 5, mixing the precursor with nano zirconium oxide, nano cerium oxide and LiOH monohydrate, wherein the lithiation ratio is 1.02, the molar ratio of metal zirconium to cerium is 1:1, and the total doping amount is 2000 ppm. Sintering the mixture for 15h at 820 ℃ in an oxygen atmosphere to obtain the cerium-zirconium co-doped NCM811 cathode material.
And (4) analyzing results:
from fig. 1(a), it can be seen that the precursor prepared in example 1 has a hollow structure, and from fig. 1(b), it can be seen that the cathode material has a hollow pore structure; the comparative examples, whether the precursor or the cathode material, did not form an effective hollow structure. The process provided by the invention can effectively prepare the precursor and the anode material with the hollow structure.
As can be seen from fig. 1(c) and fig. 1(d), the distribution of zirconium and cerium (white dots) in the precursor of example 1 is uniform, which indicates that the preparation method provided by the present invention can greatly improve the problem of the non-uniform distribution of the doping elements. In contrast, in the comparative example, the distribution was very uneven as shown in FIG. 2(c) and FIG. 2 (d).
As can be seen in fig. 3 and 4, the XRD patterns of example 1 and the comparative example are substantially identical, i.e. both components are identical. The process of the invention does not introduce other impurities, thereby reducing the use of extra pore-forming reagents and avoiding the addition of extra impurity removal procedures. Comparative example 1I(001)/I(101)>1, after the process adjustment of the present application (example 1), I can be obtained(001)/I(101)<1, lithium ion transmission in the anode material is more facilitated.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the cerium-zirconium co-doped porous structure cathode material is characterized by comprising the following steps of:
(1) preparing a ternary solution of Ni, Co and Mn, a cerium-zirconium mixed salt solution, a precipitator solution and a complexing agent solution for later use;
(2) preparing base solution and stirring;
(3) injecting a ternary solution, a cerium-zirconium mixed salt solution, a precipitator solution and a complexing agent solution into a base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size;
the reaction time of the reaction stage I is 10-30 h, the pH is controlled to be 11.2-11.8, and the ammonia concentration is controlled to be 6-10 g/L; the stirring speed is controlled at 200-600 rpm; the adjustment mode is that the flow rates of the precipitator solution and the complexing agent solution are finely adjusted to keep the pH value between 11.2 and 11.8, and the ammonia concentration is controlled between 6 and 10 g/L;
the pH value of the reaction stage II is controlled to be 10.6-11.2, and the ammonia concentration is controlled to be 8-15 g/L; the stirring speed is controlled at 150-550 rpm; the adjustment mode is that the flow of the precipitator solution is adjusted to reduce the pH value, and the flow of the complexing agent is increased to increase the ammonia concentration;
the pH and the stirring rotation speed of the reaction stage II are lower than those of the reaction stage I; the ammonia concentration of the supernatant in the reaction stage II is 2-5g/L higher than that in the stage I;
(4) centrifuging, washing, drying, screening and deironing the reacted slurry to obtain a precursor;
(5) and mixing the precursor with a lithium source, and sintering to obtain the cathode material.
2. The preparation method of the cerium-zirconium co-doped porous structure cathode material according to claim 1, characterized by comprising the following steps: the ternary solution is a sulfate solution of Ni, Co and Mn; the concentration of total metal ions in the solution is 1-3 mol/L; the precipitant solution is 20-32% of industrial liquid alkali; the complexing agent solution is ammonia water, and the mass concentration of the complexing agent solution is 15-20%.
3. The preparation method of the cerium-zirconium co-doped porous structure cathode material according to claim 1, characterized by comprising the following steps: the cerium-zirconium blended salt is selected from sulfate, nitrate or chloride of the cerium-zirconium blended salt, and the molar ratio of cerium to zirconium is 0.5-2: 1.
4. The preparation method of the cerium-zirconium co-doped porous structure cathode material according to claim 1, characterized by comprising the following steps: the preparation method of the base solution in the step (2) is as follows: adding a complexing agent solution into pure water in the atmosphere of nitrogen, and adjusting the pH value by using a precipitator solution to obtain the water-soluble organic silicon dioxide;
wherein the pH value of the base solution is controlled to be 11-12, the ammonia concentration is 6-10g/L, the temperature is 40-80 ℃, and the stirring speed is 200-600 rpm.
5. The preparation method of the cerium-zirconium co-doped porous structure cathode material according to claim 1, characterized by comprising the following steps: the flow rate of the ternary solution in the step (3) is 100-600L/h, the flow rate of the cerium-zirconium mixed salt solution is 30-200L/h, the flow rate of the precipitator solution is 30-200L/h, and the flow rate of the complexing agent solution is 10-100L/h.
6. The preparation method of the cerium-zirconium co-doped porous structure cathode material according to claim 1, characterized by comprising the following steps: the target particle size in the step (3) is D50 and reaches 3-5 mu m.
7. The cerium-zirconium co-doped porous structure cathode material is characterized in that: prepared by the method of any one of claims 1 to 6.
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| CN115321610A (en) * | 2022-08-31 | 2022-11-11 | 荆门市格林美新材料有限公司 | Zirconium-aluminum double-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof |
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