CN111439790A - High-nickel ternary cathode material and preparation method thereof - Google Patents
High-nickel ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-nickel ternary cathode material and a preparation method thereof. The method for preparing the high-nickel ternary cathode material comprises the following steps of: (1) adding a nickel-cobalt-manganese salt solution, a sodium carbonate solution, a lithium chloride solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction, thereby obtaining a first high-nickel ternary positive electrode material precursor doped with lithium carbonate; (2) introducing oxygen into the reaction system, and carrying out pre-oxidation treatment, after the pre-oxidation treatment is finished, adding a sodium carbonate solution and a lithium chloride solution into the reaction system to carry out coating reaction, so as to obtain a second high-nickel ternary cathode material precursor coated with a lithium carbonate layer; (3) and sintering the precursor of the second high-nickel ternary cathode material to obtain the high-nickel ternary cathode material. According to the method, the lithium chloride is used as a lithium source to prepare the high-nickel ternary cathode material, the raw material cost and the processing cost are low, and the prepared high-nickel ternary cathode material has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of electrode materials, in particular to a high-nickel ternary cathode material and a preparation method thereof.
Background
The development of the ternary precursor and the positive electrode material goes from NCM523 to NCM622 to NCM811, and goes through the development process from low nickel to high nickel. In the development process, the temperature of the sintering process is gradually reduced, and low-temperature sintering puts forward a new requirement on the selection of a lithium source, so that lithium carbonate suitable for a low-nickel system cannot meet the requirement of high-nickel sintering, and lithium hydroxide needs to be adopted to replace lithium carbonate as the lithium source.
However, the sintering process using lithium hydroxide as a lithium source brings new problems, the high-nickel ternary material has extremely high requirements on the quality of the sagger placed by sintering, a new sagger needs to be frequently replaced, the process operation and cost are not affected, and if the high-nickel ternary material can be sintered by using a lithium carbonate system, the problem of sagger replacement becomes better.
On the other hand, most of the existing processes adopt a triple co-precipitation method to synthesize a high-nickel hydroxide precursor, and then adopt a physical mixing mode to add a lithium source for sintering, so that the risk of uneven material mixing exists, the requirement on material mixing operation is high, the added lithium source generally has a large particle size of about 10 μm, is not beneficial to lithium ion migration in a sintering reaction, the sintering effect is not good, and the lithium hydroxide is adopted as the lithium source, so that the raw material cost is 20-50% higher than that of lithium carbonate.
In summary, the existing methods for preparing high nickel ternary cathode materials still need to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a method for preparing a high-nickel ternary cathode material and the high-nickel ternary cathode material prepared by the method. According to the method, the lithium chloride is used as a lithium source to prepare the high-nickel ternary cathode material, the raw material cost and the processing cost are low, and the prepared high-nickel ternary cathode material has excellent electrochemical performance.
In one aspect of the invention, a method of making a high nickel ternary positive electrode material is provided. According to an embodiment of the invention, the method comprises: (1) adding a nickel-cobalt-manganese salt solution, a sodium carbonate solution, a lithium chloride solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction, thereby obtaining a first high-nickel ternary positive electrode material precursor doped with lithium carbonate; (2) introducing oxygen into the reaction system, and carrying out pre-oxidation treatment, after the pre-oxidation treatment is finished, adding a sodium carbonate solution and a lithium chloride solution into the reaction system to carry out coating reaction, so as to obtain a second high-nickel ternary cathode material precursor coated with a lithium carbonate layer; (3) and sintering the precursor of the second high-nickel ternary cathode material to obtain the high-nickel ternary cathode material.
According to the method for preparing the high-nickel ternary cathode material, in the stage of preparing the precursor through the coprecipitation reaction, the sodium carbonate solution and the lithium chloride solution are added into the reaction system at the same time, the sodium carbonate can react with the lithium chloride to generate lithium carbonate, and the lithium carbonate can be uniformly doped in the precursor, so that the first high-nickel ternary cathode material precursor doped with the lithium carbonate is obtained. And subsequently, introducing oxygen into the reaction system to oxidize the surface of the precursor, and further adding a sodium carbonate solution and a lithium chloride solution to enable lithium carbonate generated by the reaction of the sodium carbonate solution and the lithium chloride solution to form a coating layer on the surface of the first high-nickel ternary cathode material precursor. According to the method, in the preparation stage of the precursor, lithium chloride is used as a lithium source, lithium ions are introduced into the precursor, lithium carbonate is used for doping and coating the precursor at the same time, the second high-nickel ternary cathode material can meet the sintering requirement of a high-nickel system under the synergistic effect of doping and coating, and the high-nickel ternary cathode material product can be obtained after sintering treatment. On the other hand, the lithium ions are introduced into the precursor by the method, so that the traditional physical material mixing process is omitted, the lithium carbonate introduced by the method has small particle size, the lithium carbonate is very favorable for the migration of the lithium ions in the sintering process, and the utilization rate of the lithium is high and can reach 90% or higher. In addition, the method avoids the use of lithium hydroxide, directly reduces the cost of raw materials, reduces the replacement frequency of the saggars in the sintering process and effectively reduces the processing cost.
In addition, the method for preparing the high-nickel ternary cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the total concentration of the nickel salt, the cobalt salt and the manganese salt in the nickel-cobalt-manganese salt solution is 0.5-1.5 mol/L.
In some embodiments of the invention, the concentration of the sodium carbonate solution is 0.5-1.5 mol/L.
In some embodiments of the invention, the concentration of the lithium chloride solution is 8-15 mol/L.
In some embodiments of the invention, the precipitant is a sodium hydroxide solution or a sodium carbonate solution with a concentration of 5-10 mol/L.
In some embodiments of the invention, the complexing agent is an ammonia water solution with a concentration of 8-12 mol/L.
In some embodiments of the invention, the reaction conditions of the synthesis reaction include a stirring rotation speed of 500-1000 rpm, a reaction temperature of 50-70 ℃, a pH value of a reaction system of 10.5-12.5, a solid content of 100-350 g/L in the reaction system, and a reaction time of 5-30 h.
In some embodiments of the invention, in the pre-oxidation treatment, the flow rate of oxygen is 60-100L/h, the treatment time is 10-20 min, and the temperature is 90-100 ℃.
In some embodiments of the invention, the reaction conditions of the coating reaction include: the reaction temperature is 90-100 ℃, the reaction time is 6-8 h, and the pH value of the reaction system is 9.0-10.5.
In some embodiments of the present invention, the sintering process comprises a first sintering process performed at 700 to 950 ℃ for 8 to 20 hours and a second sintering process performed at 550 to 650 ℃ for 8 to 12 hours.
In some embodiments of the present invention, the thickness of the lithium carbonate layer (i.e., the lithium carbonate layer coated on the surface of the first high-nickel ternary positive electrode material precursor) is 0.5-2 μm.
In some embodiments of the invention, the molar amount of lithium ions in the high-nickel ternary cathode material is 1.00 to 1.15 times that of the precursor. The molar amount of the lithium ions refers to the total molar amount of the lithium ions doped and coated in the material.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method for preparing the high-nickel ternary cathode material in the embodiment. Therefore, the high-nickel ternary cathode material is low in raw material cost and processing cost and has excellent electrochemical performance.
In some embodiments of the invention, the high nickel ternary positive electrode material has a composition represented by formula (I),
NiXCoYMn1-X-Y(OH)2·aLi2CO3(I)
in formula (1), 80% < X < 95%, 1% < Y < 15%, 1.0< a < 1.15.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method for preparing a high nickel ternary positive electrode material according to one embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a method of making a high nickel ternary positive electrode material is provided. Referring to fig. 1, according to an embodiment of the invention, the method comprises:
s100: preparing to obtain a first high-nickel ternary cathode material precursor
In the step, a nickel-cobalt-manganese salt solution, a sodium carbonate solution, a lithium chloride solution, a precipitator and a complexing agent are added into a reaction base solution for synthetic reaction, so as to obtain a first high-nickel ternary cathode material precursor doped with lithium carbonate. According to the embodiment of the invention, sodium carbonate and lithium chloride can react to generate lithium carbonate after entering a reaction system, and the lithium carbonate can be uniformly doped in the high-nickel ternary cathode material precursor along with the progress of the coprecipitation reaction. The size of lithium hydroxide adopted in the preparation process of the conventional high-nickel ternary cathode material is generally about 10 mu m, while the size of lithium carbonate obtained by the method is in the micro-nano level (less than 1 mu m), and the size of lithium carbonate is far lower than that of a conventional lithium hydroxide source, so that the lithium carbonate is very favorable for the migration of lithium ions in the subsequent sintering process.
According to some embodiments of the present invention, the reaction base solution can be prepared by dissolving 90% of theoretical amount of lithium chloride in water and adjusting the pH value to 10.5-12.5 with alkali solution. The nickel-cobalt-manganese salt solution can be prepared by dissolving a nickel salt, a cobalt salt, and a manganese salt in water in a ratio required for a high-nickel ternary positive electrode material (for example, a molar ratio of Ni: Co: Mn is 80 to 95:1 to 15), and specific types of the metal salt are not particularly limited, and for example, a sulfate, a nitrate, a hydrochloride, or the like can be selected.
According to some embodiments of the present invention, in the nickel-cobalt-manganese salt solution, the total concentration of nickel salt, cobalt salt, and manganese salt is 0.5 to 1.5 mol/L (e.g., 0.5 mol/L, 0.75 mol/L, 1.0 mol/L1, 1.5 mol/L, 1.25 mol/L, 1.5 mol/L, etc.), the concentration of the sodium carbonate solution is 0.5 to 1.5 mol/L (e.g., 0.5 mol/L, 0.75 mol/L, 1.0 mol/L, 1.5 mol/L, 1.25 mol/L, 1.5 mol/L, etc.), the concentration of the lithium chloride solution is 8 to 15 mol/L1 (e.g., 8 mol/L, 9 mol/L, 10 mol/364, 12 mol/L, 12 mol/3614 mol/L, 14 mol/3614 mol/L, etc.), the concentration of the complexing agent is preferably a high-concentration of sodium hydroxide, such as a precipitation agent, a lithium hydroxide solution, a high-quality complexing agent, a precipitation.
According to some embodiments of the present invention, the reaction conditions of the above synthesis reaction include a stirring rotation speed of 500 to 1000rpm (e.g., 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, etc.), a reaction temperature of 50 to 70 ℃ (e.g., 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, etc.), a pH of the reaction system of 10.5 to 12.5 (e.g., 10.5, 11.0, 11.5, 12.5, etc.), a solid content of the reaction system of 100 to 350 g/L (e.g., 100 g/L, 150 g/L, 200 g/L, 250 g/L, 300 g/L, 350 g/L, etc.), and a reaction time of 5 to 30h (e.g., 5h, 10h, 15h, 20h, 25h, 30h, etc.).
S200: preparing to obtain a first high-nickel ternary cathode material precursor
In the step, oxygen is introduced into the reaction system to carry out pre-oxidation treatment. And after the pre-oxidation treatment is finished, adding a sodium carbonate solution and a lithium chloride solution into the reaction system for coating reaction to obtain a second high-nickel ternary cathode material precursor coated with a lithium carbonate layer. Through letting in oxygen in the reaction system, can be with the surface oxidation of first high nickel ternary cathode material, and then, add sodium carbonate solution and lithium chloride solution to the reaction system further, lithium carbonate that the two reactions generated can wrap the surface formation coating of first high nickel ternary cathode material, and the inside even lithium carbonate that is doped of second high nickel ternary cathode material precursor that obtains, and the surface cladding has the lithium carbonate layer. Under the synergistic effect of doping and cladding, the second high-nickel ternary cathode material can meet the firing requirement of a high-nickel system, and a high-nickel ternary cathode material product can be obtained through subsequent sintering treatment. And due to the synergistic effect of lithium doping and cladding, the high-nickel ternary cathode material has better electrochemical performance.
According to some embodiments of the present invention, in the pre-oxidation treatment, the oxygen flow rate is 60 to 100L/h (e.g., 60L/h, 70L/h, 80L/h, 90L/h, 100L/h, etc.), the treatment time is 10 to 20min (e.g., 10min, 15min, 20min, etc.), and the temperature is 90 to 100 ℃ (e.g., 90 ℃, 95 ℃, 100 ℃, etc.).
According to some embodiments of the invention, the reaction conditions of the above coating reaction include: the reaction temperature is 90-100 ℃ (e.g. 90 ℃, 95 ℃, 100 ℃) and the reaction time is 6-8 h (e.g. 6h, 6.5h, 7h, 7.5h, 8h, etc.), and the pH value of the reaction system is 9.0-10.5 (e.g. 9.0, 9.5, 10.0, 10.5, etc.). Thereby, the formation of the lithium carbonate layer can be further facilitated.
According to some embodiments of the present invention, the thickness of the lithium carbonate layer (i.e. the lithium carbonate layer coated on the surface of the first high-nickel ternary positive electrode material precursor) is 0.5 to 2 μm (e.g. 0.5 μm, 1 μm, 1.5 μm, 2 μm, etc.).
S300: sintering treatment
In the step, sintering treatment is carried out on the precursor of the second high-nickel ternary cathode material, so as to obtain the high-nickel ternary cathode material. And the second high-nickel ternary positive electrode material precursor is doped with uniform lithium carbonate, and the outer surface of the second high-nickel ternary positive electrode material precursor is provided with a lithium carbonate coating layer. Sintering the precursor of the second high-nickel ternary cathode material to finish the sintering of the high-nickel ternary cathode material. And due to the synergistic effect of lithium doping and cladding, the high-nickel ternary cathode material has better electrochemical performance.
According to some embodiments of the present invention, the sintering process includes a first sintering process and a second sintering process, the first sintering process can be performed at 700-950 ℃ for 8-20 h, and the second sintering process can be performed at 550-650 ℃ for 8-12 h. Therefore, the sintering effect of the precursor of the second high-nickel ternary cathode material can be further improved, and the electrochemical performance of the high-nickel ternary cathode material product can be further improved.
In another aspect of the invention, a high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the high-nickel ternary cathode material is prepared by the method for preparing the high-nickel ternary cathode material in the embodiment. Therefore, the high-nickel ternary cathode material is low in raw material cost and processing cost and has excellent electrochemical performance.
In some embodiments of the present invention, the high nickel ternary positive electrode material has a composition represented by formula (I),
NiXCoYMn1-X-Y(OH)2·aLi2CO3(I)
in formula (1), 80% < X < 95%, 1% < Y < 15%, 1.0< a < 1.15.
In addition, it should be noted that all the features and advantages described above for the "method for preparing a high nickel ternary cathode material" are also applicable to the "high nickel ternary cathode material", and are not described in detail herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
(I) synthetic reaction
Respectively weighing nickel nitrate, cobalt nitrate and manganese nitrate according to the molar ratio of Ni to Co to Mn of 8:1:1, dissolving in water to prepare a nickel-cobalt-manganese salt solution, adjusting the concentration to 1.5 mol/L, and marking as a solution A.
An 8 mol/L solution of sodium hydroxide was prepared and designated as solution B.
An aqueous ammonia solution of 10 mol/L was prepared and designated as solution C.
A15 mol/L solution of lithium chloride was prepared and designated as solution D.
A1 mol/L solution of sodium carbonate was prepared and designated as solution E.
Adding 2.5L pure water and 90% of lithium chloride in theoretical amount as base solution into a 5L reaction kettle, adding a proper amount of alkali liquor to adjust the pH of the reaction base solution to 11.6, then adding the solution A, the solution B, the solution C, the solution D and the solution E into the reaction kettle in parallel, controlling the rotation speed to be 500rpm and the temperature to be 60 ℃, adjusting the solution flow, controlling the pH of the system to be 11.6 +/-0.05, controlling the solid content of slurry to be 200 g/L, controlling the feeding speed to be 200m L/h, and reacting for 20h to prepare the first high-nickel ternary cathode material precursor doped with lithium carbonate.
(II) coating reaction
After the reaction in the step (I) is finished, heating the system to 95 ℃, introducing oxygen for 15min at the flow rate of 100L/h, then simultaneously adding a solution D and a solution E with the theoretical amount of 20% in a concurrent flow manner, continuously reacting for 10h, maintaining the pH value of the system at 9.5 in the reaction process, overflowing the reaction material to an ageing tank after the reaction is finished, centrifugally washing, controlling the moisture content of a wet material to be 20-25%, and drying to obtain a second high-nickel ternary positive electrode material precursor, wherein the average thickness of a lithium carbonate layer on the surface of the second high-nickel ternary positive electrode material precursor is 0.9 mu m, and the average particle size of the internal hydroxide high-nickel precursor is 4 mu m.
(III) sintering treatment
And (3) carrying out first sintering treatment (800 ℃, 15h) on the second high-nickel ternary cathode material precursor prepared in the step (II), crushing the product, and carrying out second sintering treatment (600 ℃, 6h) to obtain the high-nickel ternary cathode material product.
The prepared high-nickel ternary cathode material product is used for electricity deduction assembly, the electrochemical performance is detected, the gram capacity of an obtained electricity deduction sample at 0.1 ℃ is 208-213 mA.h, and the first effect is 90%.
Example 2
(I) synthetic reaction
Respectively weighing nickel chloride, cobalt chloride and manganese chloride according to the molar ratio of Ni to Co to Mn of 88:9:3, dissolving the nickel chloride, the cobalt chloride and the manganese chloride in water to prepare a nickel-cobalt-manganese salt solution, adjusting the concentration to 1.0 mol/L, and marking as a solution A.
A6 mol/L sodium hydroxide solution was prepared and designated as solution B.
A12 mol/L ammonia solution was prepared and designated as solution C.
A12 mol/L solution of lithium chloride was prepared and designated as solution D.
A1.5 mol/L solution of sodium carbonate was prepared and designated as solution E.
Adding 2.5L pure water and 90% of lithium chloride in theoretical amount as base solution into a 5L reaction kettle, adding a proper amount of alkali liquor to adjust the pH of the reaction base solution to 11.9, then adding the solution A, the solution B, the solution C, the solution D and the solution E into the reaction kettle in parallel, controlling the rotation speed to be 600rpm and the temperature to be 55 ℃, adjusting the solution flow, controlling the pH of the system to be 11.9 +/-0.05, controlling the solid content of slurry to be 200 g/L, controlling the feeding speed to be 300m L/h, and reacting for 15h to prepare the first high-nickel ternary cathode material precursor doped with lithium carbonate.
(II) coating reaction
After the reaction in the step (I) is finished, heating the system to 95 ℃, introducing oxygen for 15min at the flow rate of 80L/h, then simultaneously adding a solution D and a solution E with the theoretical amount of 30% in a concurrent flow manner, continuously reacting for 8h, maintaining the pH value of the system at 10.0 in the reaction process, overflowing the reaction material to an ageing tank after the reaction is finished, centrifugally washing, controlling the moisture content of a wet material to be 20-25%, and drying to obtain a second high-nickel ternary positive electrode material precursor, wherein the average thickness of a lithium carbonate layer on the surface of the second high-nickel ternary positive electrode material precursor is 1.5 microns, and the average particle size of the internal hydroxide high-nickel precursor is 3 microns.
(III) sintering treatment
And (3) carrying out first sintering treatment (800 ℃, 15h) on the second high-nickel ternary cathode material precursor prepared in the step (II), crushing the product, and carrying out second sintering treatment (600 ℃, 6h) to obtain the high-nickel ternary cathode material product.
The prepared high-nickel ternary cathode material product is used for electricity deduction assembly, the electrochemical performance is detected, the gram capacity of an obtained electricity deduction sample at 0.1 ℃ is 210-215 mA.h, and the first effect is 88%.
Example 3
(I) synthetic reaction
Nickel sulfate, cobalt sulfate and manganese sulfate are respectively weighed according to the molar ratio of Ni to Co to Mn of 95:3:2, dissolved in water to prepare a nickel-cobalt-manganese salt solution, the concentration is adjusted to 0.5 mol/L, and the solution is marked as solution A.
A5 mol/L sodium hydroxide solution was prepared and designated as solution B.
An aqueous ammonia solution of 8 mol/L was prepared and designated as solution C.
A10 mol/L solution of lithium chloride was prepared and designated as solution D.
A0.8 mol/L solution of sodium carbonate was prepared and designated as solution E.
Adding 2.5L pure water and 90% of lithium chloride in theoretical amount as base solution into a 5L reaction kettle, adding a proper amount of alkali liquor to adjust the pH of the reaction base solution to 12.1, then adding the solution A, the solution B, the solution C, the solution D and the solution E into the reaction kettle in parallel, controlling the rotation speed to be 700rpm and the temperature to be 60 ℃, adjusting the solution flow, controlling the pH of the system to be 12.1 +/-0.05, controlling the solid content of slurry to be 300 g/L, controlling the feeding speed to be 250m L/h, and reacting for 18h to prepare the first high-nickel ternary cathode material precursor doped with lithium carbonate.
(II) coating reaction
After the reaction in the step (I) is finished, heating the system to 95 ℃, introducing oxygen for 15min at the flow rate of 60L/h, then simultaneously adding 35% of theoretical solution D and solution E in parallel flow, continuously reacting for 6h, maintaining the pH of the system at 9.0 in the reaction process, overflowing the reaction material to an ageing tank after the reaction is finished, centrifugally washing, controlling the moisture content of wet materials to be 20-25%, and drying to obtain a second high-nickel ternary positive electrode material precursor, wherein the average thickness of a lithium carbonate layer on the surface of the second high-nickel ternary positive electrode material precursor is 1.5 microns, and the average particle size of the internal hydroxide high-nickel precursor is 3 microns.
(III) sintering treatment
And (3) carrying out first sintering treatment (750 ℃, 15h) on the second high-nickel ternary cathode material precursor prepared in the step (II), crushing the product, and carrying out second sintering treatment (600 ℃, 6h) to obtain the high-nickel ternary cathode material product.
The prepared high-nickel ternary cathode material product is used for electricity deduction assembly, the electrochemical performance is detected, the gram capacity of an obtained electricity deduction sample at 0.1 ℃ is 212-215 mA.h, and the first effect is 87%.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a high-nickel ternary cathode material is characterized by comprising the following steps of:
(1) adding a nickel-cobalt-manganese salt solution, a sodium carbonate solution, a lithium chloride solution, a precipitator and a complexing agent into the reaction base solution to carry out synthetic reaction, thereby obtaining a first high-nickel ternary positive electrode material precursor doped with lithium carbonate;
(2) introducing oxygen into the reaction system, and carrying out pre-oxidation treatment, after the pre-oxidation treatment is finished, adding a sodium carbonate solution and a lithium chloride solution into the reaction system to carry out coating reaction, so as to obtain a second high-nickel ternary cathode material precursor coated with a lithium carbonate layer;
(3) and sintering the precursor of the second high-nickel ternary cathode material to obtain the high-nickel ternary cathode material.
2. The method of claim 1, wherein the total concentration of nickel salt, cobalt salt and manganese salt in the nickel-cobalt-manganese salt solution is 0.5-1.5 mol/L;
optionally, the concentration of the sodium carbonate solution is 0.5-1.5 mol/L;
optionally, the concentration of the lithium chloride solution is 8-15 mol/L;
optionally, the precipitator is a sodium hydroxide solution or a sodium carbonate solution with the concentration of 5-10 mol/L;
optionally, the complexing agent is an ammonia water solution with the concentration of 8-12 mol/L.
3. The method as claimed in claim 1, wherein the reaction conditions of the synthesis reaction include a stirring speed of 500-1000 rpm, a reaction temperature of 50-70 ℃, a pH value of a reaction system of 10.5-12.5, a solid content of 100-350 g/L in the reaction system, and a reaction time of 5-30 h.
4. The method according to claim 1, wherein in the pre-oxidation treatment, the flow rate of oxygen is 60-100L/h, the treatment time is 10-20 min, and the temperature is 90-100 ℃.
5. The method of claim 1, wherein the reaction conditions of the coating reaction comprise: the reaction temperature is 90-100 ℃, the reaction time is 6-8 h, and the pH value of the reaction system is 9.0-10.5.
6. The method according to claim 1, wherein the sintering treatment comprises a first sintering treatment and a second sintering treatment, the first sintering treatment is performed at 700-950 ℃ for 8-20 hours, and the second sintering treatment is performed at 550-650 ℃ for 8-12 hours.
7. The method of claim 1, wherein the lithium carbonate layer has a thickness of 0.5 to 2 μm.
8. The method according to claim 1, wherein the molar amount of lithium ions in the high-nickel ternary positive electrode material is 1.00 to 1.15 times the molar amount of the precursor.
9. A high-nickel ternary cathode material, which is prepared by the method of any one of claims 1 to 8.
10. The high-nickel ternary positive electrode material according to claim 9, having a composition represented by formula (I),
NiXCoYMn1-X-Y(OH)2·aLi2CO3(I)
in formula (1), 80% < X < 95%, 1% < Y < 15%, 1.0< a < 1.15.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490428A (en) * | 2020-12-02 | 2021-03-12 | 惠州亿纬锂能股份有限公司 | Pretreatment method of ternary precursor, product and application thereof |
| CN112993242A (en) * | 2021-05-11 | 2021-06-18 | 蜂巢能源科技有限公司 | Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material |
| CN113422040A (en) * | 2021-07-02 | 2021-09-21 | 青岛多元锂业有限公司 | Preparation method of medium-high nickel ternary material subjected to pre-oxidation treatment of precursor and lithium salt |
| CN113479941A (en) * | 2021-07-02 | 2021-10-08 | 青岛新正锂业有限公司 | Preparation method of medium-high nickel ternary material |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355159A (en) * | 2008-09-17 | 2009-01-28 | 金瑞新材料科技股份有限公司 | Method for preparing lithium ion battery anode material nickle cobalt lithium manganate |
| CN103682309A (en) * | 2013-12-02 | 2014-03-26 | 厦门钨业股份有限公司 | Preparation method of cathode active material of lithium ion battery |
| CN107359323A (en) * | 2017-06-22 | 2017-11-17 | 芜湖浙鑫新能源有限公司 | A kind of lithium-rich manganese-based anode material being prepared based on full element Direct precipitation and preparation method thereof |
| CN108511746A (en) * | 2018-03-02 | 2018-09-07 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified nickelic tertiary cathode material of pre-oxidation |
| CN108545786A (en) * | 2018-03-22 | 2018-09-18 | 杭州金马新能源科技有限公司 | A kind of preparation method of high-energy nickel cobalt manganese compound lithium ion positive electrode |
| CN108649195A (en) * | 2018-04-28 | 2018-10-12 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary lithium battery material of polythiophene base and preparation method |
| CN109461907A (en) * | 2018-10-09 | 2019-03-12 | 郑州中科新兴产业技术研究院 | A kind of preparation method of nickelic tertiary cathode material |
| CN109809500A (en) * | 2019-03-07 | 2019-05-28 | 南京航空航天大学 | Nickelic tertiary cathode material preparation method based on presoma pre-oxidation and air cleaning |
| CN110282665A (en) * | 2019-07-04 | 2019-09-27 | 成都尤尼瑞克科技有限公司 | A kind of anode material of lithium battery presoma and preparation method thereof with mesoscopic structure |
| CN110380040A (en) * | 2019-07-26 | 2019-10-25 | 浙江帕瓦新能源股份有限公司 | A kind of Moist chemical synthesis mixes the preparation method of the lithium ion battery ternary precursor of lithium |
-
2020
- 2020-04-22 CN CN202010321915.8A patent/CN111439790B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101355159A (en) * | 2008-09-17 | 2009-01-28 | 金瑞新材料科技股份有限公司 | Method for preparing lithium ion battery anode material nickle cobalt lithium manganate |
| CN103682309A (en) * | 2013-12-02 | 2014-03-26 | 厦门钨业股份有限公司 | Preparation method of cathode active material of lithium ion battery |
| CN107359323A (en) * | 2017-06-22 | 2017-11-17 | 芜湖浙鑫新能源有限公司 | A kind of lithium-rich manganese-based anode material being prepared based on full element Direct precipitation and preparation method thereof |
| CN108511746A (en) * | 2018-03-02 | 2018-09-07 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of the modified nickelic tertiary cathode material of pre-oxidation |
| CN108545786A (en) * | 2018-03-22 | 2018-09-18 | 杭州金马新能源科技有限公司 | A kind of preparation method of high-energy nickel cobalt manganese compound lithium ion positive electrode |
| CN108649195A (en) * | 2018-04-28 | 2018-10-12 | 成都新柯力化工科技有限公司 | A kind of nickelic ternary lithium battery material of polythiophene base and preparation method |
| CN109461907A (en) * | 2018-10-09 | 2019-03-12 | 郑州中科新兴产业技术研究院 | A kind of preparation method of nickelic tertiary cathode material |
| CN109809500A (en) * | 2019-03-07 | 2019-05-28 | 南京航空航天大学 | Nickelic tertiary cathode material preparation method based on presoma pre-oxidation and air cleaning |
| CN110282665A (en) * | 2019-07-04 | 2019-09-27 | 成都尤尼瑞克科技有限公司 | A kind of anode material of lithium battery presoma and preparation method thereof with mesoscopic structure |
| CN110380040A (en) * | 2019-07-26 | 2019-10-25 | 浙江帕瓦新能源股份有限公司 | A kind of Moist chemical synthesis mixes the preparation method of the lithium ion battery ternary precursor of lithium |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112490428A (en) * | 2020-12-02 | 2021-03-12 | 惠州亿纬锂能股份有限公司 | Pretreatment method of ternary precursor, product and application thereof |
| CN112993242A (en) * | 2021-05-11 | 2021-06-18 | 蜂巢能源科技有限公司 | Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material |
| CN112993242B (en) * | 2021-05-11 | 2021-10-12 | 蜂巢能源科技有限公司 | Nickel-cobalt-manganese positive electrode material and recovery method of waste nickel-cobalt-manganese positive electrode material |
| WO2022237102A1 (en) * | 2021-05-11 | 2022-11-17 | 蜂巢能源科技股份有限公司 | Recycling method for nickel-cobalt-manganese positive electrode material and waste nickel-cobalt-manganese positive electrode material |
| CN113422040A (en) * | 2021-07-02 | 2021-09-21 | 青岛多元锂业有限公司 | Preparation method of medium-high nickel ternary material subjected to pre-oxidation treatment of precursor and lithium salt |
| CN113479941A (en) * | 2021-07-02 | 2021-10-08 | 青岛新正锂业有限公司 | Preparation method of medium-high nickel ternary material |
| CN115954479A (en) * | 2023-03-10 | 2023-04-11 | 四川新能源汽车创新中心有限公司 | Positive electrode material, preparation method thereof and solid-state battery |
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