CN112382739A - Preparation method of nickel cobalt lithium manganate ternary positive electrode material with surface coated and modified - Google Patents

Preparation method of nickel cobalt lithium manganate ternary positive electrode material with surface coated and modified Download PDF

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CN112382739A
CN112382739A CN201911086223.3A CN201911086223A CN112382739A CN 112382739 A CN112382739 A CN 112382739A CN 201911086223 A CN201911086223 A CN 201911086223A CN 112382739 A CN112382739 A CN 112382739A
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nickel
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李崇
王迪
王慧萍
方向乾
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Shaanxi Rainbow New Materials Co ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract

The invention relates to a preparation method of a surface-coated modified nickel cobalt lithium manganate ternary positive electrode material, which is used for coating a surface alumina layer by a fluidized bed-chemical deposition method and comprises LiNiCobMncO 2 and a coating layer attached to the surface of the LiNiCobMncO 2. The molar ratio of the lithium, the nickel, the cobalt and the manganese is 1.02-1.12, wherein a is the ratio of a to b to c, a is more than or equal to 0.5, b and c are more than 0, and a + b + c is 1. The invention has the main beneficial effects that the material prepared by the method has good rate capability, and simultaneously, the normal-temperature cycle performance of the battery is obviously improved.

Description

Preparation method of nickel cobalt lithium manganate ternary positive electrode material with surface coated and modified
The technical field is as follows:
the invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified.
Background art:
since the discovery of the ternary cathode material (NCM), the lithium ion battery has attracted much attention of researchers due to its high capacity (up to 270mAh/g theoretical capacity), excellent safety performance, low cost and other factors. However, the nickel-cobalt-manganese ternary material generally has the following problems: firstly, cations are easy to mix and discharge, so that lithium is separated out; secondly, the rate performance is slightly poorer than that of materials such as lithium cobaltate and the like, and the cycle performance needs to be improved; and poor compatibility with electrolytes. The surface coating technology is widely applied to the modification research of nickel-cobalt-manganese ternary materials, so that the dissolution of metal ions can be effectively relieved, the corrosion of HF to active substances is reduced, and the cycle performance of the battery is improved. However, how to distribute the coating material on the surface of the nickel-cobalt-manganese ternary material more uniformly and exert the coating effect to the maximum extent, so that the nickel-cobalt-manganese ternary material has excellent rate performance and keeps good cycle performance, and the method is a hot problem in the research of the cathode material in the lithium battery industry at present. Therefore, how to select an effective coating material and a preparation method thereof becomes a bottleneck in solving the above various problems.
Common preparation methods of the nickel-cobalt-manganese ternary cathode material include a coprecipitation method, a solid-phase method, a template method, a spray drying method, a solvothermal method, a sol-gel method, a hydrothermal method and the like, and the coprecipitation method and the solid-phase method are mainly used. Patent CN107240684A reports a preparation method and product of a surface modified lithium battery high nickel cathode material, which includes: putting high-nickel anode material powder into a reaction cavity of an atomic layer deposition system, vacuumizing the reaction cavity, and controlling the temperature and pressure of the cavity; introduction of N2Taking away the excessive reaction source in the reaction cavity; introducing water to react with the reaction source, and depositing on the surface of the high-nickel anode material to obtain an oxide film; introduction of N2Taking away the excess water in the reaction cavity; and repeating the steps to obtain the surface modified high-nickel cathode material of the lithium battery. The preparation method has the characteristics of simplicity, easiness in operation, easiness in controlling the thickness of the coating layer and the like, but the surface reaction of atomic layer deposition has self-limitation, the cost is higher, and the preparation period is long.
The invention content is as follows:
in order to overcome the defects of the prior art, the invention aims to provide a preparation method of a surface-coated modified nickel cobalt manganese acid lithium ternary positive electrode material, which can be used for preparing a nickel cobalt manganese acid lithium ternary material with high cycle retention rate and good rate capability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for preparing the surface-coated modified Ni-Co-Mn acid lithium ternary positive electrode material includes coating the surface of Al oxide layer by fluidized-bed chemical deposition method, including LiNiaCobMncO2And a coating layer attached to the surface thereof; the coating layer is Al2O3(ii) a The molar ratio of the lithium, the nickel, the cobalt and the manganese is 1.02-1.12, wherein a is the ratio of a to b to c, a is more than or equal to 0.5, b and c are more than 0, and a + b + c is 1.
The coating layer Al2O3The thickness of (2) is 0.01-25nm, and the mass fraction of the coating layer is 0.01-10%, preferably 0.05-5%.
The lithium source is Li2CO3Or LiOH. H2O。
A preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified comprises the following steps:
(1) synthesis of nickel-cobalt-manganese ternary material precursor
According to the formula (n) (Ni): n (Co): weighing oxysalts (two or three of sulfate, acetate and nitrate) of the substances with the mass ratio of (a), (b) and (c) of 0-0.12, wherein a is more than or equal to 0.5, and a + b + c is 1, and adding deionized water, wherein the mass ratio of the oxysalts to the deionized water is 1: (1-8), heating and stirring the prepared solution in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, adding 0.2-2L of 0.5-2 mol/L NaOH solution, simultaneously dripping 0.1-2 mol/L ammonia water to control the pH value of the solution to be 8-12, aging the solution for 12-25 hours after the reaction is fully performed, performing vacuum filtration and washing, and placing the precipitate in a drying oven at the temperature of 100-120 ℃ for vacuum drying for 4-8 hours to obtain a nickel-cobalt-manganese ternary material precursor;
(2) coating of precursor samples
Introducing nitrogen carrying trimethylaluminum into a fluidized bed reactor suspending precursor particles, controlling the pressure in a reaction cavity to reach 5-8 mbar, controlling the temperature of the reactor at 150-.
(3) Preparation of the sintered product
Mixing the precursor obtained in the step (2) and a lithium source according to the mass ratio of 1.02-1.12: 1, uniformly ball-milling, collecting, and sintering in a muffle furnace in two stages: the first stage is a pre-sintering stage, the temperature is increased from room temperature to 350-550 ℃, and sintering is carried out in the air for 6-10 hours; and the second stage is a solid-phase reaction stage, heating to 800-980 ℃, sintering for 8-12 hours in an air/high-purity oxygen atmosphere, cooling to room temperature along with a furnace, crushing, and sieving with a 300-mesh sieve to obtain the nickel cobalt lithium manganate ternary sample with the surface coated and modified.
The invention has the main beneficial effects that:
coated nano-Al2O3Can form a protective film to reduce the corrosion of the electrolyte to the base material, thereby improving the cycle performance of the material. The material prepared by the method has good rate performance, and simultaneously, the normal-temperature cycle performance of the battery is obviously improved.
Description of the drawings:
FIG. 1 discloses a flow chart of a first embodiment of the present invention;
FIG. 2 discloses a flow chart of a second embodiment of the present invention;
fig. 3 discloses a flow chart of a third embodiment of the invention.
The specific implementation mode is as follows:
in order to make the technical means, creation features, achievement objects and effects of the present invention easy to understand, the following examples are taken to illustrate the preparation of NCM523, NCM622, and NCM811 to further clarify the present invention.
Referring to FIG. 1, FIG. 1 is a flow chart of a first embodiment
The first embodiment is as follows:
a preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified comprises the following steps:
(S1) Synthesis of NCM523 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): n (Mn): accurately weighing 0.475mol of nickel sulfate, 0.19mol of cobalt acetate and 0.285mol of manganese acetate in a mass ratio of 0.5:0.2:0.3, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in a water bath at 80 ℃ for 2 hours after the solution is prepared, mixing the solution with 1.0mol/L NaOH solution, simultaneously dripping 1.5mol/L ammonia water to control the pH of the solution to be 9-10, and aging the solution for 20 hours after the reaction is fully carried out. After vacuum filtration and washing, the precipitate is placed in an oven at 100 ℃ for vacuum drying for 4 hours to obtain a precursor of NCM 523.
(S2) coating of precursor sample
Introducing nitrogen carrying trimethylaluminum into a fluidized bed reactor suspending precursor particles, controlling the pressure in a reaction cavity to reach 5-6 mbar, controlling the temperature of the reactor at 150-.
(S3) preparation of sintered product
Step one, the precursor obtained in the step (2) and Li2CO3The materials are mixed and ball milled uniformly according to the mass ratio of 1.08:1, and the mixture is preferably ground in a planetary ball mill for 2 hours at the rotating speed of 1000 r/min.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out in the air for 6 hours; and the second stage is a solid-phase reaction stage, the temperature is raised to 920 ℃, the mixture is sintered for 12 hours in the air atmosphere, the mixture is cooled to room temperature along with a furnace, and the NCM523 sample with the modified surface coating is obtained after crushing and 300-mesh sieving.
Referring to FIG. 2, FIG. 2 is a flow chart of a second embodiment
Example two:
a preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified comprises the following steps:
(S1) Synthesis of NCM622 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): accurately weighing 0.57mol of nickel sulfate, 0.19mol of cobalt acetate and 0.19mol of manganese acetate according to the mass ratio of n (Mn) to 0.6:0.2:0.2, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in a water bath at 80 ℃ for 2 hours after the solution is prepared, mixing the solution with 1.0mol/L NaOH solution, simultaneously dripping 1.5mol/L ammonia water to control the pH of the solution to be 9-10, and aging the solution for 20 hours after the reaction is fully carried out. After vacuum filtration and washing, the precipitate is placed in an oven at 100 ℃ for vacuum drying for 4 hours to obtain the precursor of NCM 622.
(S2) coating of precursor sample
Introducing nitrogen carrying trimethylaluminum into a fluidized bed reactor suspending precursor particles, controlling the pressure in a reaction cavity to reach 5-6 mbar, controlling the temperature of the reactor at 150-.
(S3) preparation of sintered product
Step one, the precursor obtained in the step (2) and LiOH & H2O is mixed and ball milled uniformly according to the mass ratio of 1.08:1, preferably in a planetary ball mill, at the rotation speed of 800r/min for 4 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 450 ℃, and sintering is carried out in oxygen for 6 hours; and the second stage is a solid-phase reaction stage, the temperature is raised to 870 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and the NCM622 sample with the surface coated and modified is obtained after crushing and 300-mesh sieving.
Referring to FIG. 3, FIG. 3 is a flow chart of a third embodiment
Example three:
a preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified comprises the following steps:
(S1) Synthesis of NCM811 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): accurately weighing 0.76mol of nickel sulfate, 0.095mol of cobalt acetate and 0.095mol of manganese acetate in the mass ratio of n (Mn) to 0.8:0.1:0.1, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in a water bath at 80 ℃ for 2 hours after the solution is prepared, mixing the solution with 1mol/L NaOH solution, simultaneously dripping 1.5mol/L ammonia water to control the pH of the solution to be 9-10, and aging the solution for 20 hours after the reaction is fully carried out. After vacuum filtration and washing, the precipitate is placed in an oven at 100 ℃ for vacuum drying for 4 hours to obtain the precursor of NCM 811.
(S2) coating of precursor sample
Introducing nitrogen carrying trimethylaluminum into a fluidized bed reactor suspending precursor particles, controlling the pressure in a reaction cavity to reach 5-6 mbar, controlling the temperature of the reactor at 150-.
(S3) preparation of sintered product
Step one, the precursor obtained in the step (2) and LiOH & H2O is mixed and ball milled uniformly according to the mass ratio of 1.08:1, preferably in a planetary ball mill at the rotation speed of 600r/min for 6 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 350 ℃, and sintering is carried out for 6 hours in an oxygen atmosphere; and the second stage is a solid-phase reaction stage, the temperature is raised to 800 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and the NCM811 sample with the modified surface is obtained after crushing and 300-mesh sieving.
Comparative example one:
(1) synthesis of conventional NCM523 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): accurately weighing 0.475mol of nickel sulfate, 0.19mol of cobalt acetate and 0.285mol of manganese acetate in the mass ratio of n (Mn) to 0.5:0.2:0.3, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in a water bath at 80 ℃ for 2 hours after the solution is prepared, mixing the solution with 1mol/L NaOH solution, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging the solution for 20 hours after the reaction is fully carried out. After vacuum filtration and washing, the precipitate is placed in a drying oven with the temperature of 100 ℃ for vacuum drying for 4 hours, and the precursor Ni of the conventional nickel-cobalt-manganese ternary material is obtained0.5Co0.2Mn0.3(OH)2。
(2) Preparation of conventional NCM523 materials
Step one, the precursor obtained in the step (1) and LiOH & H2O is mixed and ball milled uniformly according to the mass ratio of 1.08:1, preferably in a planetary ball mill, at the rotation speed of 1000r/min for 2 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out in the air for 6 hours; the second stage is a solid phase reaction stage, the temperature is raised to 920 ℃, the mixture is sintered for 12 hours in the air atmosphere, the mixture is cooled to the room temperature along with the furnace, and the conventional nickel-cobalt-manganese ternary material LiNi is obtained after crushing and 300-mesh sieving0.5Co0.2Mn0.3O2。
Comparative example two:
(1) synthesis of conventional NCM622 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): accurately weighing 0.57mol of nickel sulfate, 0.19mol of cobalt acetate and 0.19mol of manganese acetate according to the mass ratio of n (Mn) to 0.6:0.2:0.2, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in a water bath at 80 ℃ for 2 hours after the solution is prepared, mixing the solution with 1mol/L NaOH solution, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging the solution for 20 hours after the reaction is fully carried out. Vacuum filtering,After washing, the precipitate is placed in an oven at 100 ℃ for vacuum drying for 4 hours to obtain the precursor Ni of the conventional nickel-cobalt-manganese ternary material0.6Co0.2Mn0.2(OH)2。
(2) Preparation of conventional NCM622 Material
Step one, the precursor obtained in the step (1) and Li2OH is mixed according to the mass ratio of 1.08:1 and is ball milled uniformly, preferably in a planetary ball mill, the rotating speed is 800r/min, and the milling time is 4 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out for 6 hours in an oxygen atmosphere; the second stage is a solid phase reaction stage, the temperature is raised to 870 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with a furnace, and the mixture is crushed and sieved by a 300-mesh sieve to obtain the conventional nickel-cobalt-manganese ternary material LiNi0.6Co0.2Mn0.2O2。
Comparative example three:
(1) synthesis of conventional NCM811 precursor
Nickel sulfate, cobalt acetate and manganese acetate are used as raw materials, and the raw materials are mixed according to the formula of n (Ni): n (Co): accurately weighing 0.76mol of nickel sulfate, 0.095mol of cobalt acetate and 0.095mol of manganese acetate in the mass ratio of n (Mn) to 0.8:0.1:0.1, placing the materials in a beaker, and adding deionized water, wherein the mass ratio of the oxysalt to the deionized water is 1: (1-8), heating and stirring the solution in water bath at 80 ℃ for 2 hours after preparing the solution, and mixing the solution with 1mol/L of Na2CO3Mixing the solutions, simultaneously dripping 1.0mol/L ammonia water to control the pH of the solution to be 9-10, and aging for 20 hours after the reaction is full. After vacuum filtration and washing, the precipitate is placed in a drying oven with the temperature of 100 ℃ for vacuum drying for 4 hours, and the precursor Ni of the conventional nickel-cobalt-manganese ternary material is obtained0.8Co0.1Mn0.1(OH)2。
(2) Preparation of conventional NCM811 Material
Step one, the precursor obtained in the step (1) and LiOH & H2O is mixed and ball milled uniformly according to the mass ratio of 1.08:1, preferably in a planetary ball mill at the rotation speed of 600r/min for 6 hours.
Step two, collecting the uniformly mixed materials and sintering the materials in a muffle furnace in two sections: the first stage is a pre-sintering stage, the temperature is raised from room temperature to 550 ℃, and sintering is carried out for 6 hours in an oxygen atmosphere; the second stage is a solid phase reaction stage, the temperature is raised to 800 ℃, the mixture is sintered for 12 hours in an oxygen atmosphere, the mixture is cooled to room temperature along with the furnace, and the mixture is crushed and sieved by a 300-mesh sieve to obtain the conventional nickel-cobalt-manganese ternary material LiNi0.8Co0.1Mn0.1O2。
2025 buckling electricity manufacturing test was performed on the above examples and comparative examples, and the test voltage condition (3.0-4.3) V, the rate performance test condition: 0.2C, 0.5C, 1C, 2C, 5C charge and discharge for two circles respectively, and the multiplying power performance calculation method comprises the following steps: 5C discharge capacity/0.2C discharge capacity.
The first discharge specific capacity, rate capability and cycle performance data of 0.1C of the charging of the ternary samples of comparative examples 1-3 and examples 1-3 are given in the table I.
First discharge specific capacity of 0.2C, rate capability and cycle performance of the samples in Table I, comparative example and example
Figure BDA0002265488840000111
The results show that the surface coating of Al is realized by the fluidized bed-chemical deposition method2O3Compared with the 0.1C initial discharge specific capacity of a conventional sample, the ternary material has small change, but the rate capability and the cycle performance in the electrical property of the ternary material after coating modification are also obviously improved.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.

Claims (6)

1. A preparation method of a nickel cobalt lithium manganate ternary positive electrode material with a surface coated and modified is characterized by comprising the following steps: surface alumina layer coating using fluidized bed-chemical deposition, including LiNiaCobMncO2And a coating layer attached to the surface thereof.
2. The preparation method according to claim 1, wherein the molar ratio of the lithium, the nickel, the cobalt and the manganese is 1.02-1.12: a: b: c, wherein a is more than or equal to 0.5, b and c are more than 0, and a + b + c is 1.
3. The method according to claim 1, wherein the coating layer is Al2O3。
4. The method according to claim 2, wherein said Al is2O3The thickness of (2) is 0.01-25nm, and the mass fraction of the coating layer is 0.01-10%, preferably 0.05-5%.
5. The method according to claim 1, wherein the lithium source is Li2CO3Or LiOH. H2O。
6. The preparation method of the nickel cobalt lithium manganate ternary positive electrode material with the surface coated and modified is characterized by comprising the following steps:
step S1, synthesizing nickel-cobalt-manganese ternary material precursor
According to the formula (n) (Ni): n (Co): weighing oxysalts (two or three of sulfate, acetate and nitrate) of the substances with the mass ratio of (a), (b) and (c) of 0-0.12, wherein a is more than or equal to 0.5, and a + b + c is 1, and adding deionized water, wherein the mass ratio of the oxysalts to the deionized water is 1: (1-8), heating and stirring the prepared solution in a water bath at the temperature of 60-80 ℃ for 0.5-2 hours, adding 0.2-2L of 0.5-2 mol/L NaOH solution, simultaneously dripping 0.1-2 mol/L ammonia water to control the pH value of the solution to be 8-12, aging the solution for 12-25 hours after the reaction is fully performed, performing vacuum filtration and washing, and placing the precipitate in a drying oven at the temperature of 100-120 ℃ for vacuum drying for 4-8 hours to obtain a nickel-cobalt-manganese ternary material precursor;
step S2, coating of precursor sample
Introducing nitrogen carrying trimethylaluminum into a fluidized bed reactor suspending precursor particles, controlling the pressure in a reaction cavity to reach 5-8 mbar, controlling the temperature of the reactor at 150-.
Step S3, preparation of sintered product
And (3) mixing the precursor obtained in the step (S1) and a lithium source according to the mass ratio of 1.02-1.12: 1, uniformly ball-milling, collecting, and sintering in a muffle furnace in two stages: the first stage is a pre-sintering stage, the temperature is increased from room temperature to 350-550 ℃, and sintering is carried out in the air for 6-10 hours; and the second stage is a solid-phase reaction stage, heating to 800-980 ℃, sintering for 8-12 hours in an air/high-purity oxygen atmosphere, cooling to room temperature along with a furnace, crushing, and sieving with a 300-mesh sieve to obtain the nickel cobalt lithium manganate ternary sample with the surface coated and modified.
CN201911086223.3A 2019-11-08 2019-11-08 Preparation method of nickel cobalt lithium manganate ternary positive electrode material with surface coated and modified Pending CN112382739A (en)

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