CN111276680B - Precursor cathode material with hollow interior and core-shell structure and preparation method thereof - Google Patents
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a precursor cathode material with a hollow interior and a core-shell structure and a preparation method thereof. The method comprises the following steps: (1) preparing a binary or ternary solution, a precipitator solution and a complexing agent solution for later use; (2) preparing base solution and stirring; (3) injecting a binary or ternary solution, a precipitator solution and a complexing agent solution into the base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size; (4) centrifuging, 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. According to the process, the pH of a reaction system is controlled and adjusted through adding of a precipitator and a complexing agent solution and controlling of flow rate in different reaction stages, and stirring rotating speeds in different stages are adjusted to prepare the cathode material with a hollow interior, no extra pore-forming reagent is needed, and industrial mass production can be realized.
Description
Technical Field
The invention belongs to the field of electrode materials and the field of electrochemical energy storage, and particularly relates to a precursor cathode material with a hollow interior and a core-shell structure 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.
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.
CN201610978071.8 discloses a high-rate long-life cathode material and a preparation method thereof, wherein PEG with large molecular weight is used as a surfactant to obtain a precursor with a porous structure.
CN 109616664a 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 prior art methods for preparing porous materials either add pore formers or surfactants or introduce organic species to carbonize during the subsequent sintering process to form the pore structure. However, in actual industrial production, the requirement of customers on impurities of products is extremely strict, even carbon has extremely strict index requirements, and after the substances are added, higher requirements are put forward for subsequent impurity removal, and the process and the cost are increased. Meanwhile, the addition of other substances increases the production process and auxiliary materials, and the manufacturing cost of the product is further increased.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a precursor cathode material with a hollow core-shell structure, which does not need to add a pore-forming agent additionally or select a specific organic raw material or an additive so as to form a pore structure through carbonization in subsequent sintering.
The preparation of the precursor with the hollow structure is realized by controlling the process conditions of the two reaction stages. In the first stage, primary particles are refined through high pH and high stirring speed, and the ammonia concentration is increased to accelerate the growth speed, so that the particle agglomeration is looser. In the second stage, the pH value and the stirring speed are reduced to slowly coarsen primary particles, and the ammonia concentration is reduced to enable the particles to be more tightly agglomerated. When the anode material is sintered, because the primary particles of the core and the shell are different, the primary particles of the core are fine and are agglomerated and loose, the primary particles firstly migrate outwards during sintering, and the primary particles of the shell are coarse, the agglomeration is more compact and higher than the sintering temperature required by the core, and finally, cavities are left on the surface of the anode material.
The scheme provided by the invention is as follows:
a preparation method of a precursor cathode material with a hollow interior and a core-shell structure comprises the following steps:
(1) preparing a binary or ternary solution, a precipitator solution and a complexing agent solution for later use;
(2) preparing base solution and stirring;
(3) injecting a binary or ternary solution, a precipitator solution and a complexing agent solution into the base solution, carrying out stage I and stage II reactions, and stopping feeding until the reaction reaches a target particle size;
(4) centrifuging, 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 binary solution is a sulfate solution containing Ni and Co; 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.
Further, the precipitant solution is 20-32% of industrial liquid caustic soda; the complexing agent solution is ammonia water, and the mass concentration of the complexing agent solution is 15-20%.
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 12.0-12.5, the ammonia concentration is 2-20 g/L, the temperature is 40-80 ℃, and the stirring speed is 200-600 rpm.
Further, the flow rate of the binary or ternary solution in the step (3) is 100-500L/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 10-20 h, the pH is controlled to be 11.8-12.3, and the ammonia concentration is controlled to be 5-15 g/L; the stirring speed was controlled at 200-600 rpm. The adjustment was made by fine-tuning the precipitant solution and aqueous ammonia flow to maintain the pH and ammonia concentration controlled within the ranges.
Further, the pH value of the reaction stage II in the step (3) is controlled to be 11.0-12.0, and the ammonia concentration is controlled to be 3-8 g/L; the stirring speed was controlled at 150-550 rpm. The adjustment mode is to adjust the flow of the precipitator solution to reduce the pH value and reduce the flow of the complexing agent solution to reduce the ammonia concentration.
Further, the pH value of the reaction stage II is lower than that of the reaction stage I, and the stirring rotation speed is 40-80rpm lower than that of the reaction stage I; the supernatant ammonia concentration of reaction stage II was 40-60% of stage I.
Further, the target particle size D50 in the step (3) is 3-5 μm.
The invention also aims to provide a precursor cathode material with a hollow interior and a core-shell structure prepared by the method,
the invention has the beneficial effects that:
1. pore-forming agents or surfactants are not needed, the pH of a reaction system is adjusted only by adding precipitants and controlling the flow rate at different reaction stages, precursors with different inner and outer primary particle structures and core-shell structures are prepared by adjusting and controlling the stirring speed and the ammonia concentration at different stages, and cavities are formed in the anode material after sintering.
2. The process mode can be applied to the mass production of binary, ternary and quaternary precursors such as NC, NCM, NCA, NCMA and the like, can be applied to industrial mass production, does not increase the production cost and is beneficial to cost control.
3. 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.
4. Under the condition of not increasing the production cost, the structure of the precursor and the anode material thereof is changed, and the rate capability of the anode 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 a precursor cathode material with an internal hollow structure core-shell structure.
Drawings
Fig. 1 is an SEM image of the precursor and the cathode material prepared in example 1; FIG. 1(a) shows a precursor, and FIG. 1(b) shows a positive electrode material;
fig. 2 is an SEM image of the precursor and the positive electrode material prepared in the comparative example; fig. 2(a) is a precursor, and fig. 2(b) is a positive electrode material;
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 described with reference to specific embodiments, to which the present invention is not at all limited.
The following percentages are by mass unless otherwise specified.
Example 1
Step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a binary solution with a total metal concentration of 2mol/L according to a metal molar ratio of 7:1: 2; adopting 32% industrial liquid alkali as precipitant solution; 17% ammonia water as complexing agent solution.
And 2, adding pure water into the reaction kettle, and introducing nitrogen as protective gas. The temperature is raised to 64-66 ℃, and the stirring speed is controlled at 500 rpm. Adding 17% ammonia water to adjust the ammonia concentration of the base solution to 9-10g/L, and adjusting the pH of the base solution to 12.1-12.3 by using 32% industrial liquid alkali.
stage I: controlling the pH value of a reaction system to be 11.8-12.1 and the ammonia concentration to be 9-10g/L by fine adjustment of the flow rates of liquid caustic soda and ammonia water, and reacting for 20 hours;
stage II: adjusting the flow rate of the liquid caustic soda to 145L/h, reducing the pH value to 11.2-11.6, adjusting the stirring speed to 450rpm, simultaneously reducing the flow rate of the ammonia water to 25L/h, adjusting the ammonia concentration to 4-5g/L, and continuing to react until D50 reaches 3.5um, and stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening and removing iron to obtain the NCM712 precursor with the special structure.
And 5, mixing the precursor with lithium hydroxide, and sintering for 15h at 780 ℃ in an oxygen atmosphere to obtain the NCM712 electrode material with a hollow interior.
Example 2
Step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into ternary solution with total metal concentration of 2mol/L according to the metal molar ratio of 92:4: 4; adopting 32% industrial liquid alkali as precipitant solution; 17% ammonia water as complexing agent solution.
And 2, adding pure water into the reaction kettle, and introducing nitrogen as protective gas. The temperature is raised to 59-61 ℃, and the stirring speed is controlled at 450 rpm. Adding 17% ammonia water to adjust the ammonia concentration of the base solution to 11-12g/L, and adjusting the pH of the base solution to 12.2-12.4 by using 32% industrial liquid alkali.
And 3, simultaneously adding the ternary solution, the precipitator solution and the complexing agent solution into the reaction kettle at the speed of 400L/h, 164L/h and 55L/h respectively to carry out the reaction of stage I, II:
stage I: the pH value of a reaction system is controlled to be 12.0-12.2 and the ammonia concentration is controlled to be 11-12g/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 154L/h, reducing the pH value to 11.4-11.8, adjusting the stirring speed to 400rpm, simultaneously reducing the flow rate of ammonia water to 28L/h, adjusting the ammonia concentration to 5-6g/L, and continuously reacting until the D50 reaches 4.0um, and stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening and removing iron to obtain the precursor NCM920404 with the special structure.
And 5, mixing the precursor with lithium hydroxide, and sintering for 18h at 750 ℃ in an oxygen atmosphere to obtain the NCM920404 cathode material with the hollow interior.
Example 3
Step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into ternary solution with total metal concentration of 2mol/L according to a metal molar ratio of 90:5: 5; adopting 32% industrial liquid alkali as precipitant solution; 17% ammonia water as complexing agent solution.
And 2, adding pure water into the reaction kettle, and introducing nitrogen as protective gas. The temperature is increased to 63-65 ℃, and the stirring speed is controlled at 380 rpm. Adding 17% ammonia water to adjust the ammonia concentration of the base solution to 12-15g/L, and adjusting the pH of the base solution to 12.0-12.2 by using 32% industrial liquid alkali.
And 3, simultaneously adding the ternary solution, the precipitator solution and the complexing agent solution into the reaction kettle at the speed of 500L/h, 170L/h and 60L/h respectively to carry out the reaction of stage I, II:
stage I: the pH value of a reaction system is controlled to be 11.8-12.0 and the ammonia concentration is controlled to be 12-15g/L by fine adjustment of the flow rates of liquid caustic soda and ammonia water, and the reaction is carried out for 10 hours;
stage II: adjusting the flow rate of liquid caustic soda to 160L/h, reducing the pH value to 11.0-11.4, adjusting the stirring speed to 300rpm, simultaneously reducing the flow rate of ammonia to 30L/h, adjusting the ammonia concentration to 6-7g/L, and continuously reacting until the D50 reaches 3.8um, and stopping feeding.
And 4, centrifugally washing the slurry in the reaction kettle, drying, screening and removing iron to obtain the precursor of the NCM900505 with the special structure.
And 5, mixing the precursor with lithium hydroxide, and sintering for 20h at 730 ℃ in an oxygen atmosphere to obtain the NCM900505 cathode material with a hollow interior.
Comparative example
Step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into ternary solution with total metal concentration of 2mol/L according to a metal molar ratio of 7:1: 2; adopting 32% industrial liquid alkali as precipitant solution; 17% ammonia water as complexing agent solution.
And 2, adding pure water into the reaction kettle, and introducing nitrogen as protective gas. The temperature is raised to 58-60 ℃, and the stirring speed is controlled at 500 rpm. Adding 17% ammonia water to adjust the ammonia concentration of the base solution to 8-9g/L, and adjusting the pH of the base solution to 11.6-11.8 by using 32% industrial liquid alkali.
And 3, simultaneously adding the ternary solution, the precipitator solution and the complexing agent solution into the reaction kettle at the speed of 500L/h, 160L/h and 45L/h respectively. The reaction was stopped until D50 reached 3.5 um.
And 5, carrying out centrifugal washing on the slurry in the reaction kettle, drying, screening and deironing to obtain an NCM712 precursor.
And 6, mixing the precursor with lithium hydroxide, and sintering for 15 hours at 880 ℃ in an oxygen atmosphere to obtain the NCM712 cathode material.
And (4) analyzing results:
fig. 1(a) shows that the precursor prepared in example 1 has a hollow structure, and fig. 1(b) shows that the cathode material has a hollow core-shell 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 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. A preparation method of a precursor cathode material with a hollow interior and a core-shell structure is characterized by comprising the following steps:
(1) preparing a binary or ternary solution, a precipitator solution and a complexing agent solution for later use;
the binary solution is a sulfate solution of Ni and Co; the ternary solution is a sulfate solution of Ni, Co and Mn;
(2) preparing base solution and stirring;
(3) injecting a binary or ternary solution, a precipitator solution and a complexing agent solution into the 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 10-20 h, the pH is controlled to be 11.8-12.3, and the ammonia concentration is controlled to be 5-15 g/L; the stirring speed is controlled at 200-600 rpm; the adjustment mode is that the flow rates of the precipitant solution and the ammonia water are finely adjusted to keep the pH value to be controlled at 11.8-12.3 and the ammonia concentration to be controlled at 5-15 g/L;
the pH value of the reaction stage II is controlled to be 11.0-12.0, and the ammonia concentration is controlled to be 3-8 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 solution is reduced to reduce the ammonia concentration;
the pH value of the reaction stage II is lower than that of the reaction stage I, and the stirring rotation speed is 40-80rpm lower than that of the reaction stage I; the ammonia concentration of the supernatant in the reaction stage II is 40-60% of that in the reaction stage I;
(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.
2. The preparation method of the precursor cathode material with the hollow interior and the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the concentration of total metal ions in the binary solution or the ternary solution is 1-3 mol/L.
3. The preparation method of the precursor cathode material with the hollow interior and the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: 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%.
4. The preparation method of the precursor cathode material with the hollow interior and the core-shell structure according to claim 1, wherein 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 12.0-12.5, the ammonia concentration is 2-20 g/L, the temperature is 40-80 ℃, and the stirring speed is 200-600 rpm.
5. The preparation method of the precursor cathode material with the hollow interior and the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the flow rate of the binary or ternary solution in the step (3) is 100-500L/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 precursor cathode material with the hollow interior and the core-shell structure according to claim 1, wherein the preparation method comprises the following steps: the target particle size in the step (3) is D50 and reaches 3-5 mu m.
7. A precursor cathode material with a hollow interior and a core-shell structure is characterized in that: prepared by the method of any one of steps 1-6.
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| CN112194203A (en) * | 2020-10-29 | 2021-01-08 | 格林爱科(荆门)新能源材料有限公司 | Preparation method of nickel-cobalt oxide material |
| CN112624208A (en) * | 2020-12-17 | 2021-04-09 | 厦门厦钨新能源材料股份有限公司 | Nickel-containing precursor, nickel-containing composite material, and preparation method and application thereof |
| CN113387399A (en) * | 2021-05-13 | 2021-09-14 | 北京泰丰先行新能源科技有限公司 | High-nickel ternary positive electrode material precursor and preparation method thereof |
| CN113479942A (en) * | 2021-07-01 | 2021-10-08 | 昆山宝创新能源科技有限公司 | Ternary cathode material precursor with core-shell structure, preparation method, automatic control feeding system and application thereof |
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| CN114772556B (en) * | 2022-06-20 | 2022-11-04 | 天津蓝天太阳科技有限公司 | Porous structure precursor, hollow structure oxide and application in anode material |
| CN115072804B (en) * | 2022-07-08 | 2024-02-02 | 金驰能源材料有限公司 | Method for regulating XRD diffraction intensity ratio of precursor (101) and (001) crystal faces |
| CN115092976B (en) * | 2022-07-08 | 2023-10-24 | 金驰能源材料有限公司 | Preparation method of precursor with high specific surface area and high tap density |
| CN115504521A (en) * | 2022-09-27 | 2022-12-23 | 陕西红马科技有限公司 | Precursor with controllable internal pores and preparation method of anode material of precursor |
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| CN106340638A (en) * | 2016-10-10 | 2017-01-18 | 哈尔滨工业大学 | High multiplying power lithium-enriched manganese-based anode material with double-layer hollow structure and preparation method thereof |
| CN110002515A (en) * | 2019-03-26 | 2019-07-12 | 南通金通储能动力新材料有限公司 | A kind of high capacity monocrystalline type tertiary cathode material preparation method |
| CN110330060A (en) * | 2019-07-31 | 2019-10-15 | 海南大学 | A kind of preparation method of radial structure spherical shape NCM811 type tertiary cathode material |
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