CN111170375A - Ternary positive electrode material precursor and preparation method thereof - Google Patents
Ternary positive electrode material precursor and preparation method thereof Download PDFInfo
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Abstract
The invention provides a ternary anode material precursor and a preparation method thereof, wherein the method comprises the following steps: 1) mixing a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution, wherein the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate is (1-9) to (0.5-5), so as to obtain a mixed metal salt solution; 2) dropwise mixing a mixed metal salt solution, a precipitator and a complexing agent in an inert atmosphere, and then reacting to generate a precipitate; 3) when D50 of the precipitate reaches 5-15um, introducing oxygen-containing gas to allow oxidation reaction on the surface of the precipitate, and introducing gas until the specific surface area of the precipitate reaches 5-20m2Stopping after the reaction is finished, and carrying out solid-liquid separation on a system after the oxidation reaction to obtain a ternary componentAnd (3) a positive electrode material precursor. The sulfur content of the ternary cathode material precursor prepared by the method is below 500ppm, and the obtained precursor has good appearance.
Description
Technical Field
The invention relates to a preparation method of a precursor of a ternary cathode material, belongs to the technical field of cathode materials of lithium ion batteries, and particularly relates to a preparation method of a precursor of a low-sulfur ternary cathode material.
Background
The green development is the subject of the world at present, the environmental protection has a profound influence on the fate of human beings, and the traditional energy source is turned into a new energy source. As environmental pollution increases and greenhouse effect becomes more severe, it becomes more urgent to replace the conventional fossil energy with clean energy. In order to solve the environmental problems, many countries have begun to develop new energy vehicles, and have begun to set up a fuel vehicle sale prohibition schedule, and new energy vehicles have been rapidly developed. Among new energy vehicles, lithium ion battery electric vehicles become the mainstream of new energy vehicle development at present due to the advantages of high endurance mileage, strong safety, relatively mature technology and the like.
With the continuous expansion of the demand of lithium ion batteries, consumers have higher and higher requirements on the endurance mileage of electric vehicles, and how to improve the capacity of the lithium ion batteries becomes the most concerned problem of the people at present. In the lithium ion battery, the positive electrode material directly determines the battery capacity, and the ternary positive electrode material of the lithium ion battery becomes one of the positive electrode materials with higher industrialization at present due to the advantages of high energy density and the like. In the ternary positive electrode material, the capacity of the nickel-cobalt-manganese ternary material is high, the performance of the assembled battery is good, the price of raw materials is low, the synthesis method is simple, the process is mature, and the nickel-cobalt-manganese ternary material is the key point of research and application of the current positive electrode material.
The commonly used method for synthesizing the ternary cathode material precursor is mainly a sulfate coprecipitation method, and comprises the following specific steps: mixing prepared nickel sulfate, cobalt sulfate and manganese sulfate solutions with certain concentrations according to a certain proportion, dropwise adding the mixed solutions into a reaction kettle through a feeding pump, dropwise adding a precipitator to precipitate the mixed solutions, and adding a complexing agent to control the uniformity of crystallization. The reaction liquid needs to be stirred in the dripping process, the reaction uniformity is ensured, and meanwhile, the negative feedback system controls the pH value to be stabilized at a set value through the dripping speed of the precipitator. And after the reaction is finished, centrifugally filtering the product, washing and drying to obtain the ternary material precursor.
Various physical and chemical properties of the precursor can directly influence various properties of the battery, including tap density, crystal form, particle size, specific surface area, impurity content and the like. Sulfur impurities reduce the capacity of the battery and have a large adverse effect on the cyclicity, and sulfur is present as SO in the precursor4 2-The form (b) is present in the crystal structure and is more difficult to remove by ordinary washing. Most of the techniques are to reduce SO in the precursor by alkali washing, water washing and the like4 2-The concentration can reduce the sulfur content in the precursor to a certain value; however, the precursor particles synthesized by the continuous method are compact and have small specific surface area, the detergent is difficult to reach the inside of the precursor particles, and SO in the precursor4 2-The content is reduced to a certain extent and does not change.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention controls the process parameters from the synthesis stage, and reduces the SO contained in the precursor of the ternary cathode material4 2-Further, the content of sulfur impurities in the obtained precursor is reduced.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of a ternary cathode material precursor, which comprises the following steps:
1) mixing a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution, wherein the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate is (1-9) to (0.5-5), so as to obtain a mixed metal salt solution;
2) dropwise mixing the mixed metal salt solution with a precipitator and a complexing agent in an inert atmosphere, and then reacting to generate a precipitate;
3) when D50 of the precipitate reaches 5-15um, introducing oxygen-containing gas to the precipitate to allow oxidation reaction on the surface of the precipitate, and introducing the gas until the specific surface area of the precipitate reaches 5-20m2Stopping after the reaction is carried out for a while, and carrying out solid-liquid separation on the system after the oxidation reaction to obtain a precursor of the ternary cathode material;
in the step 1), the molar ratio of the nickel sulfate, the cobalt sulfate and the manganese sulfate is preferably (3.3-9): 0.5-3.3; and/or
In the step 2), the molar ratio of the mixed metal salt solution, the complexing agent and the precipitating agent is 1 (0.5-1) to (2-2.2), preferably 1 (0.6-0.7) to (2.1-2.2); controlling the dropping speed of the precipitant to ensure that the pH value in the reaction system is 11-13; the temperature of the reaction is controlled to be 40-90 ℃, preferably 60-80 ℃.
In step 1) of the specific embodiment of the present invention, nickel sulfate, cobalt sulfate, and manganese sulfate are used as raw materials to prepare the nickel sulfate aqueous solution, and the cobalt sulfate aqueous solution and the manganese sulfate aqueous solution are prepared. The molar concentration of the mixed metal salt solution is equal to the sum of the molar concentrations of the nickel sulfate aqueous solution, the cobalt sulfate aqueous solution and the manganese sulfate aqueous solution.
In the preparation method, on the premise that the molar ratio of the mixed metal salt solution, the complexing agent and the precipitating agent is 1 (0.5-1) to (2-2.2), the solutions can be respectively dripped into a reaction kettle at a certain speed through a metering pump; in some embodiments, in step 2), the concentration of the mixed metal salt solution is 2 to 2.5mol/L, and the dropping speed of the mixed metal salt solution is 0.1 to 1.0L/h, preferably 0.1 to 0.5L/h; the complexing agent is ammonia water with the concentration of 8-14mol/L, and the dripping speed of the complexing agent is 0.007-0.313L/h, preferably 0.007-0.125L/h; the precipitant is sodium hydroxide water solution with concentration of 6-10mol/L, and the dripping speed of the precipitant is controlled to maintain the pH value in the reaction system between 11 and 13, such as 11.5, 12 and 12.5.
In a specific embodiment of the present invention, nitrogen or argon is introduced into the reaction system of step 2) to provide the inert atmosphere so as to ensure that the surface of the precipitate obtained during the dropping of each solution is not oxidized, and in some preferred embodiments, the air in the reaction system may be replaced with the above-mentioned gas before the dropping of each solution. The reaction in the step 2) is carried out under stirring, and the preferred stirring speed is 200-500r/min, so that the reaction liquid dripped into the reaction system is in a highly mixed state, can be dispersed quickly, and ensures the uniformity of the reaction.
In the specific implementation process of step 3) of the present invention, when D50 of the precipitate reaches 5-15um, an oxygen-containing gas is introduced into the precipitate to cause an oxidation reaction on the surface of the precipitate, and the specific surface area of the precipitate changes during the oxidation reaction. In some preferred embodiments, the oxygen-containing gas is selected from gases having an oxygen content of 20% by volume or more, and preferably air may be used.
D50 in the present invention means the corresponding particle size when the cumulative particle size distribution of a sample reaches 50%, and represents the average particle size of the sample.
The researchers of the invention find that when the specific surface area of the precipitate is lower, the surface compactness degree is higher, and SO in the material obtained subsequently4 2-The removal is difficult, so that the sulfur content in the precursor of the ternary cathode material is increased; when the specific surface area of the precipitate is high, the degree of surface densification is low, SO4 2-The amount of adhesion is large and it is difficult to reduce the sulfur content. The present inventors have further found that when an oxygen-containing gas is introduced to the precipitate to reach a specific surface area of 5 to 20m2And when the sulfur content is in the range of one gram, the sulfur content in the obtained ternary cathode material precursor is favorably reduced, and the sulfur content in the obtained ternary cathode material precursor is lower than 500 ppm.
In step 3) of the specific embodiment of the present invention, the solid obtained after the solid-liquid separation is further subjected to purification treatment and drying to obtain the precursor of the ternary cathode material;
in some embodiments, the system after the oxidation reaction may be subjected to solid-liquid separation, for example, centrifugation to remove mother liquor; washing solid substance obtained after solid-liquid separation with alkali liquor for 1-5 times, specifically using 0.1-2mol/L sodium hydroxide water solution; washing with water for 1-5 times; and then drying at 90-150 ℃ to obtain the ternary cathode material precursor.
The invention provides a ternary cathode material precursor, which comprises the following components: nixCoyMnz(OH)2Wherein, 0<x is less than 1, y is more than or equal to 0.05 and less than 1, z is more than or equal to 0.05 and less than 1, x + y + z is 1, and the sulfur content in the precursor of the ternary cathode material is less than 500 ppm; in some preferred embodiments, the preparation method can be adopted.
The composition of the precursor of the ternary cathode material is as follows: nixCoyMnz(OH)2In the above formula, x is preferably 0.33 to 0.9, y is preferably 0.05 to 0.33, and z is preferably 0.05 to 0.33.
D50 in the precursor of the ternary cathode material is 7-20um, preferably 8-12 um.
By adopting the technical scheme, the method has the following technical effects:
the preparation method of the invention reduces SO in the precipitate by controlling the pH value of the system to be 11-13 in the step 2) of the preparation process4 2-The sulfur content in the precursor is further reduced; and in the reaction process, the molar ratio of each solution and the reaction temperature (40-90 ℃) are controlled, so that the reaction efficiency is improved, the complexing effect of the complexing agent is ensured, and the obtained precursor has a good shape.
In the preparation step 3) of the invention, when the D50 of the precipitate reaches 5-15um, the oxidation reaction is carried out on the surface area of the precipitate by introducing gas containing oxygen into the system; at the same time, the change in specific surface area on the surface of the precipitate was examined until it reached 5-20m2Stopping introducing the gas after the volume per gram, so that the D50 of the obtained ternary cathode material precursor reaches 7-20 um.
Drawings
FIG. 1: SEM image of the ternary positive electrode material precursor prepared in example 1;
FIG. 2: the particle size distribution diagram of the precursor of the ternary cathode material prepared in example 1;
FIG. 3: SEM image of the precursor of the ternary positive electrode material prepared in comparative example 1;
FIG. 4: the particle size distribution diagram of the precursor of the ternary cathode material prepared in comparative example 1.
Detailed Description
The following test methods were used in the examples of the present invention:
(1) sulfur content: measuring the sulfur content in the precursor by adopting an inductively coupled plasma atomic emission spectrometry;
(2) d50 test: using a Malvern laser particle size analyzer (model: Mastersizer 3000) to carry out particle size detection on the precursor;
(3) specific surface area: detecting the specific surface area by adopting a nitrogen adsorption method and using a Beschard specific surface instrument (model: 3H-2000 BET-A);
(4) and (3) precursor composition determination: and determining the content of nickel, cobalt and manganese in the precursor by adopting the industry standard YS/T1006.2-2014.
The starting materials used in the examples are, unless otherwise stated, conventional commercial products and the purity of the starting materials is analytical.
Example 1
1) Nickel sulfate aqueous solution, cobalt sulfate aqueous solution and manganese sulfate aqueous solution are mixed according to a molar ratio of 8: 1: 1 to obtain a mixed metal salt solution (2.2 mol/L);
2) introducing nitrogen into a reaction kettle to replace air in the kettle, adjusting the stirring speed in the reaction kettle to be 400r/min, dropwise adding the mixed metal salt solution into the reaction kettle at the speed of 0.4L/h and ammonia water (9mol/L) at the speed of 0.088L/h, controlling the dropwise adding speed of the sodium hydroxide aqueous solution (8mol/L) to maintain the pH value in the kettle at 12.0, and reacting at 65 ℃ to generate precipitates in the reaction process;
3) when the granularity D50 of the precipitate is increased to 10um, air is introduced into the reaction kettle, and the specific surface area of the precipitate reaches 15m after 50min2Stopping ventilation, centrifuging to remove the mother liquor to obtain a solid, washing the solid for 3 times by using a 1mol/L sodium hydroxide aqueous solution, and then washing for 2 times by using deionized water; and then, putting the obtained solid into an oven to be dried at 120 ℃ to obtain a precursor 1 of the ternary cathode material.
Measured by threeThe composition of the precursor 1 of the meta-anode material is Ni0.8Co0.1Mn0.1(OH)2The sulfur content was 428ppm, and D50 of the ternary positive electrode material precursor 1 was 11 um.
The scanning electron microscope image of the ternary cathode material precursor 1 is shown in fig. 1, and the surface of the obtained precursor is smooth; the particle size distribution is shown in FIG. 2, where the particle size distribution is narrower.
Example 2
1) Mixing a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution according to a molar ratio of 83: 12: 5 to obtain a mixed metal salt solution (2 mol/L);
2) introducing nitrogen into a reaction kettle to replace air in the kettle, adjusting the stirring speed in the reaction kettle to be 500r/min, dropwise adding the mixed metal salt solution into the reaction kettle at the speed of 0.2L/h and ammonia water (14mol/L) at the speed of 0.018L/h, controlling the dropwise adding speed of sodium hydroxide aqueous solution (9mol/L) to maintain the pH value in the kettle at 12.8, and reacting at 70 ℃ to generate precipitates in the reaction process;
3) when the granularity D50 of the precipitate is increased to 12um, air is introduced into the reaction kettle, and the specific surface area of the precipitate reaches 12m after 40min2Stopping aeration, centrifuging to remove mother liquor to obtain solid, washing the solid for 1 time by using 1.5mol/L sodium hydroxide aqueous solution, and then washing for 5 times by using deionized water; and then, putting the obtained solid into an oven to be dried at the temperature of 130 ℃ to obtain a precursor 2 of the ternary cathode material.
The composition of the precursor 2 of the ternary cathode material is Ni through measurement0.83Co0.12Mn0.05(OH)2The sulfur content was 391ppm, and the D50 of the ternary positive electrode material precursor 2 was 15 um.
Example 3
1) Nickel sulfate aqueous solution, cobalt sulfate aqueous solution and manganese sulfate aqueous solution are mixed according to a molar ratio of 70: 15: 15 to obtain a mixed metal salt solution (2 mol/L);
2) introducing nitrogen into a reaction kettle to replace air in the kettle, adjusting the stirring speed in the reaction kettle to 350r/min, dropwise adding the mixed metal salt solution into the reaction kettle at the speed of 0.45L/h and ammonia water (10mol/L) at the speed of 0.069L/h, controlling the dropwise adding speed of the sodium hydroxide aqueous solution (8mol/L) to maintain the pH value in the kettle at 11.5, and reacting at 70 ℃ to generate precipitates in the reaction process;
3) when the granularity D50 of the precipitate is increased to 7um, air is introduced into the reaction kettle, and the specific surface area of the precipitate reaches 10m after 30min2Stopping ventilation, centrifuging to remove the mother liquor to obtain a solid, washing the solid for 1 time by using 1mol/L sodium hydroxide aqueous solution, and then washing for 5 times by using deionized water; and then, putting the obtained solid into an oven to be dried at the temperature of 110 ℃ to obtain a precursor 3 of the ternary cathode material.
Through determination, the composition of the precursor 3 of the ternary cathode material is Ni0.7Co0.15Mn0.15(OH)2The sulfur content was 455ppm, and D50 of the ternary positive electrode material precursor 3 was 8.5 um.
Example 4
1) Mixing a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution according to a molar ratio of 6: 2: 2 to obtain a mixed metal salt solution (2 mol/L);
2) introducing nitrogen into a reaction kettle to replace air in the kettle, adjusting the stirring speed in the reaction kettle to be 300r/min, dropwise adding the mixed metal salt solution into the reaction kettle at the speed of 0.5L/h and ammonia water (12mol/L) at the speed of 0.075L/h, controlling the dropwise adding speed of the sodium hydroxide aqueous solution (10mol/L) to maintain the pH value in the kettle at 12.5, and reacting at 70 ℃ to generate precipitates in the reaction process;
3) when the granularity D50 of the precipitate is increased to 8um, air is introduced into the reaction kettle, and the specific surface area of the precipitate reaches 18m after 60min2Stopping ventilation, centrifuging to remove the mother liquor to obtain a solid, washing the solid for 1 time by using 1mol/L sodium hydroxide aqueous solution, and then washing for 5 times by using deionized water; and then, putting the obtained solid into an oven to be dried at 120 ℃ to obtain a ternary cathode material precursor 4.
Through determination, the composition of the precursor 3 of the ternary cathode material is Ni0.6Co0.2Mn0.2(OH)2The sulfur content was 425ppm, and the D50 of the ternary positive electrode material precursor 4 was 10 um.
Comparative example 1
This comparative example differs from example 1 in that: in the step 2), the dropping speed of the mixed metal salt solution (2.2mol/L) is 0.4L/h, and the dropping speed of the ammonia water (9mol/L) is 0.352L/h, so as to obtain the ternary cathode material precursor 5.
The composition of the precursor 5 of the ternary cathode material is determined to be Ni0.73Co0.13Mn0.14(OH)2The sulfur content was 1335ppm, and the D50 of the ternary positive electrode material precursor 1 was 10.5 um.
The scanning electron microscope image of the ternary cathode material precursor 5 is shown in fig. 3, and the surface of the obtained precursor is rough; the particle size distribution is shown in FIG. 4, where the particle size distribution is broad.
Comparative example 2
This comparative example differs from example 1 in that: in the step 2), the reaction temperature is 30 ℃, and a ternary cathode material precursor 6 is obtained;
through determination, the composition of the precursor 6 of the ternary cathode material is Ni0.83Co0.12Mn0.05(OH)2The sulfur content was 2421ppm, and D50 of the ternary cathode material precursor 6 was 11 um.
Comparative example 3
This comparative example differs from example 1 in that: in the step 2), the dropping speed of the sodium hydroxide aqueous solution is controlled to maintain the pH value in the reaction kettle at 10.7, so as to obtain a precursor 7 of the ternary cathode material.
The composition of the precursor 7 of the ternary cathode material is determined to be Ni0.7Co0.15Mn0.15(OH)2The sulfur content was 1091ppm, and D50 of the ternary positive electrode material precursor 7 was 14 um.
Comparative example 4
This comparative example differs from example 1 in that: in the step 3), the specific surface area of the precipitate reaches 3m after air is introduced for 20min2Stopping ventilation per gram to obtain a ternary cathode material precursor 8.
Through determination, the composition of the precursor 8 of the ternary cathode material is Ni0.6Co0.2Mn0.2(OH)2The sulfur content was 913ppm, and D50 of the ternary positive electrode material precursor 8 was 10.5 um.
Claims (10)
1. A preparation method of a ternary cathode material precursor is characterized by comprising the following steps:
1) mixing a nickel sulfate aqueous solution, a cobalt sulfate aqueous solution and a manganese sulfate aqueous solution, wherein the molar ratio of nickel sulfate, cobalt sulfate and manganese sulfate is (1-9) to (0.5-5), so as to obtain a mixed metal salt solution;
2) dropwise mixing the mixed metal salt solution with a precipitator and a complexing agent in an inert atmosphere, and then reacting to generate a precipitate;
3) when D50 of the precipitate reaches 5-15um, introducing oxygen-containing gas to the precipitate to allow oxidation reaction on the surface of the precipitate, and introducing the gas until the specific surface area of the precipitate reaches 5-20m2Stopping after the reaction is carried out for a while, and carrying out solid-liquid separation on the system after the oxidation reaction to obtain a precursor of the ternary cathode material;
in the step 1), the molar ratio of the nickel sulfate, the cobalt sulfate and the manganese sulfate is preferably (3.3-9): 0.5-3.3; and/or
In the step 2), the molar ratio of the mixed metal salt solution, the complexing agent and the precipitating agent is 1 (0.5-1) to (2-2.2), preferably 1 (0.6-0.7) to (2.1-2.2); controlling the dropping speed of the precipitant to ensure that the pH value in the reaction system is 11-13; the temperature of the reaction is controlled to be 40-90 ℃, preferably 60-80 ℃.
2. The method according to claim 1, wherein the concentration of the mixed metal salt solution in step 2) is 2 to 2.5mol/L, and the dropping rate of the mixed metal salt solution is 0.1 to 1.0L/h, preferably 0.1 to 0.5L/h.
3. The preparation method according to claim 2, wherein in the step 2), the complexing agent is ammonia water with a concentration of 8-14mol/L, and the dropping speed of the complexing agent is 0.007-0.313L/h, preferably 0.007-0.125L/h.
4. The method according to claim 3, wherein in the step 2), the precipitant is an aqueous solution of sodium hydroxide having a concentration of 6 to 10 mol/L.
5. The production method according to claim 4, wherein nitrogen or argon is introduced into the reaction system of step 2) to provide the inert atmosphere;
the reaction is carried out with stirring, preferably at a stirring speed of 200 to 500 r/min.
6. The production method according to any one of claims 1 to 5, wherein in step 3), the oxygen-containing gas is selected from gases having an oxygen content of 20% by volume or more, preferably air.
7. The preparation method according to claim 6, wherein in step 3), the ternary cathode material precursor is obtained by purifying and drying a solid obtained after the solid-liquid separation;
preferably, the purification treatment comprises washing with alkali liquor and water for 1-5 times in sequence, wherein the alkali liquor is preferably sodium hydroxide aqueous solution with the concentration of 0.1-2 mol/L; the drying is carried out at 90-150 ℃.
8. A ternary positive electrode material precursor is characterized by comprising the following components: nixCoyMnz(OH)2Wherein, 0<x is less than 1, y is more than or equal to 0.05 and less than 1, z is more than or equal to 0.05 and less than 1, x + y + z is 1, and the sulfur content in the precursor of the ternary cathode material is less than 500 ppm;
preferably by the production method according to any one of claims 1 to 7.
9. The ternary positive electrode material precursor according to claim 8, wherein the group of ternary positive electrode material precursors isThe method comprises the following steps: nixCoyMnz(OH)2Wherein x is 0.33-0.9, y is 0.05-0.33, and z is 0.05-0.33.
10. The ternary positive electrode material precursor according to claim 9, wherein D50 in the ternary positive electrode material precursor is 7-20um, preferably 8-12 um.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113461073A (en) * | 2021-07-01 | 2021-10-01 | 广东佳纳能源科技有限公司 | Ternary precursor and preparation method and application thereof |
| CN114044542A (en) * | 2021-11-01 | 2022-02-15 | 华友新能源科技（衢州）有限公司 | Nickel-cobalt-manganese ternary precursor and preparation method thereof |
| CN114132972A (en) * | 2021-12-21 | 2022-03-04 | 天齐创锂科技(深圳)有限公司 | Method for controlling concentrated distribution of particle size of precursor of ternary cathode material |
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