CN112830527B - Precursor of hollow cathode material and preparation method thereof - Google Patents
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Abstract
The invention belongs to the field of lithium ion battery materials, and discloses a precursor of a hollow cathode material and a preparation method thereof. The precursor of the hollow cathode material with narrow particle size distribution and high specific surface area is prepared by adjusting the flow and pH of the ternary metal salt solution in the reaction process of different stages. The method has simple process, does not increase the cost on the basis of the existing mainstream discontinuous method, and is not only suitable for the manganese-containing precursor, but also suitable for the nickel-cobalt-aluminum and other manganese-free precursors.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a precursor of a hollow cathode material with narrow particle size distribution and high specific surface area and a preparation method thereof.
Background
In recent years, the energy crisis and environmental pollution problems have become more serious, and governments of various countries have begun to increase the investment in new energy automobile industry in order to reduce global carbon emission, and electric drive devices such as Hybrid Electric Vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs) and pure Electric Vehicles (EVs) equipped with lithium ion batteries have begun to gradually replace pure fuel vehicles. The ternary material has become a main anode material of the current power battery because of high energy density and good rate performance, but the traditional ternary material cannot meet the requirements of battery manufacturers on high output power and high cycle characteristics of the power battery.
Compared with the traditional ternary material, the hollow material has high output power and high cycle performance, because the hollow material has a larger hollow part in the center of the secondary particle, the contact area between the material and the electrolyte can be enlarged by immersing the electrolyte into the hollow part, and the Li is shortened+And the diffusion path is adopted, so that the internal resistance of the battery is reduced, and the output performance is improved. In addition, due to the existence of the hollow part, the volume change of the positive electrode material in the charging and discharging process can be buffered, and the effects of stabilizing the structure and improving the cycle performance are achieved. When a positive electrode material having a small specific surface area is used, the reaction between the positive electrode material and the electrolyte cannot be sufficiently ensured. In addition, when the particle size distribution of the cathode material is wide, the cathode material is selectively deteriorated due to non-uniform voltage applied to each particle, and the capacity is reduced, so that the hollow material is required to have a narrow particle size distribution and a high specific surface area in order to further improve the output characteristics and the cycle performance of the hollow material.
The positive electrode material can inherit the appearance structure and physical property index of the precursor to a great extent, so that the preparation of the hollow positive electrode material precursor is very important, and the methods for preparing the hollow material precursor in the prior art mainly comprise two types. The first is a template method, a core-shell structure precursor with a core as a template and a shell as a metal hydroxide is synthesized by introducing a template (such as carbon microspheres) to participate in a coprecipitation reaction, and the template is removed by high-temperature calcination in a sintering process to obtain a hollow cathode material, so that the generation cost is remarkably increased, the difficulty of a production process is improved, and the hollow cathode material is difficult to apply on a large scale; the second is a kernel oxidation method, previouslyIntroducing oxidizing gas or adding oxidant at the initial stage of preparing the precursor, and passing through Mn2+In order to reduce the surface energy of the system, a large number of fine primary particles are agglomerated together to form a loose aggregate, then the using amount of an oxidant is reduced or inert protective gas is introduced to react in a low-oxidation atmosphere or a non-oxidation atmosphere, the size of the primary particles is increased, the arrangement tends to be tight, so that a structure with loose inside and dense outside is formed, and when the subsequent lithium mixing and sintering are carried out, the fine primary particles at the core part shrink outwards to form a hollow structure gradually.
Patent application publication No. CN102884659A discloses a method for preparing a hollow material precursor without adding a complexing agent during the reaction process, in which inorganic acid is required to be added to regulate pH during the implementation process, in order to obtain a narrow particle size distribution, the feeding needs to be suspended for many times during the reaction process, the supernatant is drained, the reaction time is too short, and the production efficiency is insufficient.
Patent application with publication number CN112047397A discloses a preparation method of a hollow material precursor, which needs to add various polymer additives in the implementation process, thus increasing the process difficulty and production cost.
In summary, it is difficult to produce a hollow material precursor having a narrow particle diameter and a high specific surface area in a large scale and with high efficiency in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the technical problems to be solved by the invention are as follows: the precursor of the hollow cathode material with narrow particle size distribution and high specific surface area and the preparation method thereof are provided, template agent or other additional additives are not needed to be added, the synthetic reaction atmosphere is not needed to be set to be an oxidation atmosphere, the process is simple, the mass production is easy, and the industrial value is great.
The solution of the invention is realized by the following steps:
firstly, the invention provides a precursor of a hollow cathode material, and the precursor IIThe secondary particles are formed into a spheroid by agglomeration of a plurality of primary particles, and comprise an inner core part and an outer shell part which are formed by the primary particles, and the size of the primary particles of the inner core part is smaller than that of the primary particles of the outer shell part; the average particle size of the precursor is 3-5 μm, and the average particle size represents [ (D90-D10)/D50 ] of the index of the particle size distribution width]0.8 or less, preferably 0.7 or less; the specific surface area of the precursor is more than 25m2A specific surface area of more than 30m is preferred2/g。
The invention also provides a preparation method of the precursor of the hollow cathode material, which comprises the following steps:
(1) preparing a nickel-cobalt-manganese ternary metal salt solution; preparing an alkali solution;
(2) preparing a reaction kettle bottom solution, and continuously introducing inert gas into the reaction kettle;
(3) on the basis of the step (2), adding a ternary metal salt solution into the reaction kettle, carrying out the reaction of the stage I, after the pH of the solution in the reaction kettle is reduced to 8.5-11.0, increasing the flow of the ternary metal salt solution added into the reaction kettle, simultaneously adding an alkali solution, maintaining the pH of the solution in the reaction kettle within the range of 8.5-11.0, and carrying out the reaction of the stage II until the reaction slurry reaches the target particle size;
(4) and (4) filtering, aging, washing and drying the reaction slurry obtained in the step (3) to obtain the precursor of the hollow cathode material.
Further, in the step (1), the molar concentration of total metal ions in the prepared nickel-cobalt-manganese ternary metal salt solution is 1-2.5 mol/L; the concentration of the prepared alkali solution is 1-10 moL/L.
Further, in the step (2), the reaction kettle bottom liquid is prepared by the following steps: adding pure water into the reaction kettle, controlling the reaction temperature to be 40-80 ℃, and injecting an alkali solution to adjust the pH to be 11-12.5.
In the stage I reaction, only the ternary metal salt solution is added into the reaction kettle, and the pH is naturally reduced to 8.5-11.0 through the reaction of nickel, cobalt and manganese ions and hydroxide ions in the solution in the reaction kettle.
And in the stage II reaction, a ternary metal salt solution and an alkali solution are added into the reaction kettle at the same time, and the pH value is maintained within the range of 8.5-11.0 through the continuous injection of the alkali solution.
Furthermore, in the reaction process of the stage II, the flow rate of the ternary metal salt solution added into the reaction kettle is larger than that of the ternary metal salt solution added into the reaction kettle in the reaction process of the stage I.
Furthermore, in the reaction process of the stage II, the flow of the ternary metal salt solution added into the reaction kettle is increased in times.
Further, in the reaction process of the stage II, the flow rate of the ternary metal salt solution added into the reaction kettle for the first time is 50-150% of the flow rate of the ternary metal salt solution added in the reaction process of the stage I, and the flow rate of the ternary metal salt solution added into the reaction kettle for each time of increase is 50-150% of the flow rate of the previous time, and the flow rate is more preferably 50-100%.
Furthermore, in the reaction process of the stage II, the flow rate of the ternary metal salt solution added into the reaction kettle is increased for 1 to 5 times, and the preferable time is 2 to 3 times.
When the precursor particles are observed to begin to disperse through a microscope, the flow rate of the ternary metal salt solution is intermittently increased multiple times. When the flow rate of the ternary metal salt solution increased once is too large, crystal nuclei are sometimes precipitated due to rapid increase in the supersaturation degree in the solution. In addition, in order to avoid the fluctuation of the pH value caused by the frequent increase of the flow rate of the ternary metal salt solution, the flow rate is preferably controlled to be increased for 1 to 5 times, and more preferably for 2 to 3 times.
Further, in the reaction process of the stage II, when the times are more than 3, the single time interval is 15-30% of the total reaction time.
The total reaction time may be set or determined according to the desired target particle size value.
In addition, no complexing agent capable of forming complex ions with nickel, cobalt and manganese, such as ammonia, ammonium carbonate, ammonium bicarbonate and the like, is added in the reaction process of the stage I and the reaction process of the stage II.
In the invention, no alkali solution is injected in the reaction process of the stage I, and the fine particles generated in the early stage of the reaction of the stage I are agglomerated into loose agglomerates through the rapid reduction of pH. And after the pH value is reduced to be within the range of 8.5-11.0, simultaneously injecting an alkali solution and a ternary metal salt solution to enter the reaction of the stage II, setting the pH value within the range, so that the growth of crystals in the solution can be preferentially carried out without nucleation, and the newly generated primary particles can continue to grow on the aggregate formed by the reaction of the stage I, thereby obtaining the precursor with the core-outer wall structure.
In the reaction process of the stage II, the flow of the ternary metal salt solution is increased to accelerate the growth speed of precursor small particles in the solution, so that the aim of reducing the particle size distribution is fulfilled; the pH value of the reaction in the stage II is controlled in a lower range, for example, the pH value is set to 9.5, so that the prepared precursor can be refined into primary particles, and the purpose of increasing the specific surface area is achieved; however, when the pH is too low, for example, pH is less than or equal to 8.0, the primary particles are too fine, which may lead to deterioration of processability of the precursor and excessive impurities, and therefore, the pH is preferably set to a range of 8.5 to 11.0, more preferably, 9.0 to 10.5.
The precursor prepared by the method is uniformly mixed with a lithium source, and then is sintered for 2-24 hours at 650-900 ℃ in an oxidizing atmosphere, so that the cathode material with a hollow interior can be obtained.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the inner core is formed through the reaction of the stage I, the outer wall is formed through the reaction of the stage II, and the hollow material precursor is prepared without other additional additives and oxidizing atmosphere, so that the production cost is low.
(2) The invention can realize the control of the primary particle size of the precursor by controlling the pH value of the stage II reaction, thereby achieving the purpose of regulating and controlling the specific surface area of the precursor; the precursor prepared by the technical scheme provided by the invention has narrow particle size distribution and high specific surface area, fully ensures the reaction of the anode material and the electrolyte, and improves the output characteristic and the cycle performance of the hollow material.
(3) The method is suitable for precursors without manganese elements such as NCA and the like, and has wide application range.
(4) The method is simple in process and is suitable for the existing precursor production process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 shows Ni prepared in example 10.50Co0.20Mn0.30(OH)2LiNi (lithium niobate) serving as cathode material with hollow interior and obtained by sintering precursor mixed with lithium0.50Co0.20Mn0.30O2The electron microscope picture of (a).
FIG. 2 shows Ni prepared in example 10.50Co0.20Mn0.30(OH)2Electron microscopy pictures of the precursors.
FIG. 3 shows Ni prepared in example 10.50Co0.20Mn0.30(OH)2Electron microscope pictures of the cross section of the precursor.
FIG. 4 shows Ni prepared in example 30.35Co0.35Mn0.30(OH)2Electron microscopy pictures of the precursors.
FIG. 5 shows Ni prepared in example 30.35Co0.35Mn0.30(OH)2Electron microscope pictures of the cross section of the precursor.
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.
Example 1
Preparing a ternary metal salt solution of nickel sulfate, cobalt sulfate and manganese sulfate with the total metal concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 50: 20: 30, preparing 2mol/L sodium hydroxide solution. Adding pure water into a reaction kettle with the volume of 300L, controlling the temperature at 70 ℃, adjusting the pH to 11.70 by using alkali liquor, and continuously introducing nitrogen into the reaction kettle.
In the stage I reaction process, injecting a ternary metal salt solution into a reaction kettle at a flow rate of 60mL/min, controlling the reaction temperature to be 70 ℃, entering the stage II reaction after the pH value of the solution is reduced to 9.50, starting to inject a sodium hydroxide solution, maintaining the pH value of the solution within the range of 9.50 +/-0.02, increasing the flow rate of the ternary metal salt solution to 120mL/min after 6 hours of reaction, increasing the flow rate of the ternary metal salt solution to 180mL/min after 12 hours of reaction, and stopping the reaction after the particle size of a precursor reaches 3.6 mu m. And in the process of the coprecipitation reaction, discharging the supernatant solution in the reaction kettle through a physical settling tank or a concentrator. Filtering, aging, washing, drying and screening the prepared slurry to obtain Ni0.50Co0.20Mn0.30(OH)2And (5) precursor products.
The obtained Ni0.50Co0.20Mn0.30(OH)2Uniformly mixing the product with lithium carbonate, and sintering at 750 ℃ for 15h to obtain LiNi with hollow interior0.50Co0.20Mn0.30O2And (3) a positive electrode material.
FIG. 1 is a hollow interior LiNi prepared in this example0.50Co0.20Mn0.30O2FIG. 2 is an electron microscope photograph of the positive electrode material, and Ni prepared in this example0.50Co0.20Mn0.30(OH)2FIG. 3 is an electron microscope photograph of the precursor, and Ni prepared in this example0.50Co0.20Mn0.30(OH)2The electron microscope picture of the section of the precursor can be seen from the picture, the prepared precursor has an obvious inner core-outer wall structure, the size of primary particles of the inner core is smaller than that of the primary particles of the outer wall, and the anode material obtained by sintering the precursor has an internal hollow structure.
Example 2
Preparing a ternary metal salt solution of nickel sulfate, cobalt sulfate and manganese sulfate with the total metal concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 50: 20: 30, preparing 2mol/L sodium hydroxide solution. Adding pure water into a reaction kettle with the volume of 300L, controlling the temperature at 70 ℃, adjusting the pH to 11.50 by using alkali liquor, and continuously introducing nitrogen into the reaction kettle.
In the stage I reaction process, injecting a ternary metal salt solution into a reaction kettle at a flow rate of 60mL/min, controlling the reaction temperature to be 70 ℃, entering a stage II reaction after the pH value of the solution is reduced to 8.90, starting to inject a sodium hydroxide solution, maintaining the pH value of the solution within the range of 8.90 +/-0.02, increasing the flow rate of the ternary metal salt solution to 100mL/min after reacting for 6 hours, increasing the flow rate of the ternary metal salt solution to 200mL/min after 10 hours, and stopping the reaction after the particle size of a precursor reaches 4.4 mu m. And in the process of the coprecipitation reaction, discharging the supernatant solution in the reaction kettle through a physical settling tank or a concentrator. Filtering, aging, washing, drying and screening the prepared slurry to obtain Ni0.50Co0.20Mn0.30(OH)2And (5) precursor products.
Example 3
Preparing a ternary metal salt solution of nickel sulfate, cobalt sulfate and manganese sulfate with the total metal concentration of 2mol/L, wherein the molar ratio of nickel to cobalt to manganese is 35: 35: 30, preparing 2mol/L sodium hydroxide solution. Adding pure water into a reaction kettle with the volume of 100L, controlling the temperature to be 65 ℃, adjusting the pH to be 11.70 by using alkali liquor, and continuously introducing nitrogen into the reaction kettle.
In the stage I reaction process, injecting a ternary metal salt solution into a reaction kettle at a flow rate of 40mL/min, controlling the reaction temperature to be 70 ℃, entering a stage II reaction after the pH value of the solution is reduced to 8.90, starting to inject a sodium hydroxide solution, maintaining the pH value of the solution within a range of 9.8 +/-0.02, increasing the flow rate of the ternary metal salt solution to 80mL/min after the reaction is carried out for 6 hours, increasing the flow rate of the ternary metal salt solution to 120mL/min after 12 hours, and stopping the reaction after the particle size of a precursor reaches 4.3 mu m. And in the process of the coprecipitation reaction, discharging the supernatant solution in the reaction kettle through a physical settling tank or a concentrator. Filtering, aging, washing, drying and screening the prepared slurry to obtain Ni0.35Co0.35Mn0.30(OH)2And (5) precursor products.
FIG. 4 shows Ni prepared in this example0.35Co0.35Mn0.30(OH)2FIG. 5 is an electron microscope photograph of the precursor, and Ni prepared in this example0.35Co0.35Mn0.30(OH)2The electron microscope picture of the section of the precursor shows that the precursor prepared by the technical scheme of the invention has an obvious inner core-outer wall structure, and the primary particle size of the inner core is smaller than that of the outer wall.
The precursors prepared in examples 1 to 3 were further tested for physical property indexes, and the results are shown in table 1.
TABLE 1 indexes of physical properties of the precursors prepared in examples 1 to 3
As can be seen from Table 1, the specific surface area of the precursor prepared by the technical scheme of the invention is large and is 25m2The specific surface area of the precursor prepared in the example 2 is up to 47.88m2(ii)/g; in addition, the precursor prepared by the method has narrow particle size distribution, and the expression parameter of the particle size distribution is less than 0.7.
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 (8)
1. A preparation method of a hollow cathode material precursor is characterized by comprising the following steps:
(1) preparing a nickel-cobalt-manganese ternary metal salt solution; preparing an alkali solution;
(2) preparing a reaction kettle bottom solution, and continuously introducing inert gas into the reaction kettle;
(3) on the basis of the step (2), adding a ternary metal salt solution into the reaction kettle, carrying out the reaction of the stage I, increasing the flow of the ternary metal salt solution added into the reaction kettle after the pH of the solution in the reaction kettle is reduced to 8.5-11.0, simultaneously adding an alkali solution, keeping the pH of the solution in the reaction kettle at 8.5-11.0, and carrying out the reaction of the stage II until the reaction slurry reaches the target particle size;
(4) filtering, aging, washing and drying the reaction slurry obtained in the step (3) to obtain a precursor of the hollow cathode material;
the secondary particles of the precursor are agglomerated by a plurality of primary particles to form a spheroid, and the spheroid comprises an inner core part and an outer shell part which are formed by the primary particles, wherein the primary particle size of the inner core part is smaller than that of the outer shell part; the average particle size of the precursor is 3-5 μm, and the average particle size represents [ (D90-D10)/D50 ] of the index of the particle size distribution width]Below 0.8; the specific surface area of the precursor is more than 25m2/g。
2. The preparation method of claim 1, wherein in the step (1), the molar concentration of the total metal ions in the prepared nickel-cobalt-manganese ternary metal salt solution is 1-2.5 mol/L; the concentration of the prepared alkali solution is 1-10 moL/L.
3. The method according to claim 1, wherein the temperature of the bottom liquid of the reaction vessel is 40 to 80 ℃ and the pH value is 11 to 12.5.
4. The process of claim 1 wherein the flow of the ternary metal salt solution into the reactor during the stage II reaction is greater than the flow of the ternary metal salt solution into the reactor during the stage I reaction.
5. The method of claim 4, wherein the flow rate of the ternary metal salt solution fed into the reaction vessel is increased in several steps during the stage II reaction.
6. The method according to claim 5, wherein the number of times is 1 to 5 times.
7. The method of claim 5, wherein the first increased flow rate of the ternary metal salt solution into the reaction vessel is 50-150% of the flow rate of the ternary metal salt solution added during the stage I reaction, and each subsequent increased flow rate of the ternary metal salt solution into the reaction vessel is 50-150% of the previous flow rate.
8. The method of claim 6, wherein when the number of times is greater than 3, the time interval between single passes is 15 to 30% of the total reaction time.
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| CN114772658B (en) * | 2022-04-24 | 2023-10-17 | 南通金通储能动力新材料有限公司 | Precursor of positive electrode material of power lithium ion battery and preparation method thereof |
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| KR101696524B1 (en) * | 2011-06-07 | 2017-01-13 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Nickel composite hydroxide and process for producing same, positive active material for nonaqueous-electrolyte secondary battery and process for producing same, and nonaqueous-electrolyte secondary battery |
| CN103474650B (en) * | 2013-10-11 | 2015-06-17 | 哈尔滨工业大学 | Method for preparing hollow high voltage nickel manganese acid lithium anode material |
| CN103924258B (en) * | 2014-04-28 | 2016-08-24 | 中国科学院青海盐湖研究所 | The method utilizing salt lake bittern electrolytic preparation lithium hydroxide |
| JP6436335B2 (en) * | 2014-07-29 | 2018-12-12 | 住友金属鉱山株式会社 | Transition metal composite hydroxide particles, method for producing the same, and method for producing positive electrode active material for non-aqueous electrolyte secondary battery using the same |
| CN109686929B (en) * | 2018-11-29 | 2021-08-03 | 兰州金通储能动力新材料有限公司 | Nickel-cobalt-manganese ternary precursor and preparation method thereof |
| CN110921723B (en) * | 2019-12-16 | 2022-05-27 | 金驰能源材料有限公司 | Preparation method of hollow lithium ion battery anode material precursor |
| CN110931772B (en) * | 2020-02-12 | 2020-06-19 | 湖南长远锂科股份有限公司 | Preparation method of high-power type positive electrode material for lithium ion battery |
| CN111362243B (en) * | 2020-05-27 | 2020-10-27 | 湖南雅城新材料有限公司 | Preparation method of iron phosphate for lithium battery |
| CN111921561B (en) * | 2020-08-18 | 2023-06-23 | 浙江工业大学 | Hierarchical hollow structure NH 2 Preparation method of MIL-125 (Ti) desulfurization catalyst |
| CN112250091A (en) * | 2020-10-30 | 2021-01-22 | 浙江帕瓦新能源股份有限公司 | High-nickel ternary precursor, positive electrode material and preparation method |
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