CN109671924B - Preparation method of nickel-cobalt-manganese ternary cathode material - Google Patents

Preparation method of nickel-cobalt-manganese ternary cathode material Download PDF

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CN109671924B
CN109671924B CN201811444858.1A CN201811444858A CN109671924B CN 109671924 B CN109671924 B CN 109671924B CN 201811444858 A CN201811444858 A CN 201811444858A CN 109671924 B CN109671924 B CN 109671924B
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cobalt
nickel
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李佰康
朱用
王梁梁
李加闯
赵亮
袁超群
褚风辉
朱涛
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Lanzhou Kington Energy Storage Power New Material Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525Selection 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

A preparation method of a nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps: introducing a mixed gas of carbon dioxide and oxygen into a reaction device, adding a nickel-cobalt-manganese mixed solution, controlling the pH of a reaction solution to be 9.5-10.5, and preparing a core of a nickel-cobalt-manganese ternary precursor at 75-95 ℃; adjusting the reaction temperature to 45-65 ℃, and adjusting the pH of the reaction liquid to 11.5-12.5 after crystallization; adding a nickel-cobalt-manganese mixed solution and a complexing agent solution, controlling the pH of a reaction solution to be 11.5-12.5, and controlling the reaction temperature to be 45-65 ℃ to prepare a nickel-cobalt-manganese ternary precursor shell; aging and other post-treatments are carried out on the product to obtain a nickel-cobalt-manganese ternary precursor with a composite alpha and beta type core-shell structure; then ball-milling and mixing with lithium hydroxide, and sintering at high temperature to obtain a pre-sintered ternary cathode material; and sintering at high temperature to obtain the nickel-cobalt-manganese ternary cathode material. The anode material prepared by the invention has good capacity, high capacity retention rate after multiple cycles and outstanding electrochemical performance.

Description

Preparation method of nickel-cobalt-manganese ternary cathode material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a nickel-cobalt-manganese ternary cathode material.
Background
The common ternary cathode material is prepared by mixing and calcining secondary spherical particles formed by agglomeration of fine grains of nickel-cobalt-manganese hydroxide and lithium hydroxide. However, the following problems exist for high nickel ternary positive electrode materials, especially secondary spherical particles: 1. in the sintering process of the high-nickel ternary cathode material, the sintering temperature is low, so that the Li ion embedding speed is low, for secondary spherical particles with a slightly large particle size, lithium is difficult to burn into the particles due to dense primary particle accumulation, so that the lithium melting inside and outside the particles is uneven, the residual lithium of the cathode material is high, the capacity is low, and the processability of the ternary precursor is poor; 2. generally, after a battery using a ternary cathode material is subjected to multiple charge-discharge cycles, the capacity, cycle performance and safety performance of the battery are reduced. Mainly due to the following reasons: the actual charge-discharge process of the battery is that the Li ions are embedded and separated in the anode material, the anode material is separated along with the continuous embedding of the Li ions in the anode material from a microscopic angle, the crystal lattice of the anode material expands and contracts along with the Li ions, the volume of the anode material is continuously changed, the volume of primary particles forming secondary spherical particles is continuously changed macroscopically, the stress between the primary particles is continuously increased due to anisotropy, small cracks are gradually formed between the primary particles, the small cracks are gradually increased, and finally the secondary spherical particles are cracked. After the secondary spherical particles are broken, the contact area between the anode material and the electrolyte is increased, an SEI film between the anode material and the electrolyte is formed again, and the side reactions of the anode material and the electrolyte are increased. The battery capacity is reduced, the cycle performance is deteriorated, the safety performance is reduced and the like.
Disclosure of Invention
In view of the technical defects, the invention aims to provide a preparation method of a nickel-cobalt-manganese ternary cathode material.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a nickel-cobalt-manganese ternary cathode material sequentially comprises the following steps:
introducing mixed gas of carbon dioxide and oxygen into a reaction device, adding a nickel-cobalt-manganese mixed solution into the reaction device at a constant speed, simultaneously adding an alkali solution to control the pH value of a reaction solution in the reaction device to be 9.5-10.5, strongly stirring in a feeding process, and preparing a core of a nickel-cobalt-manganese ternary precursor with a core-shell structure at a reaction temperature of 75-95 ℃, wherein the core is the nickel-cobalt-manganese ternary precursor with an alpha-type structure;
step (2), adding liquid temporarily, switching the mixed gas to nitrogen, adjusting the temperature in the reaction device to 45-65 ℃, and adding an alkali solution to adjust the pH value of the reaction liquid to 11.5-12.5 after crystallization for 1-2 hours;
step (3), adding the nickel-cobalt-manganese mixed solution and the complexing agent solution into the reaction device respectively in a constant-speed parallel flow mode, simultaneously adding an alkali solution to control the pH value of a reaction solution in the reaction device to be 11.5-12.5, strongly stirring in a feeding process, controlling the reaction temperature to be 45-65 ℃, and reacting under the protection of a nitrogen atmosphere to prepare a shell of a nickel-cobalt-manganese ternary precursor with a core-shell structure, wherein the shell is a nickel-cobalt-manganese ternary precursor with a beta-type structure;
step (4), aging, liquid-solid separation, washing and drying the product obtained in the step (3) to obtain a nickel-cobalt-manganese ternary precursor with a composite alpha and beta type core-shell structure;
and (5) ball-milling and mixing the core-shell structure nickel-cobalt-manganese ternary precursor obtained in the step (4) with lithium hydroxide, wherein the molar ratio of the sum of nickel, cobalt and manganese in the core-shell structure nickel-cobalt-manganese ternary precursor to the lithium hydroxide is 1: 1.05, sintering for 6-10 hours at 400-600 ℃ in an air atmosphere to obtain a pre-sintered ternary cathode material;
and (6) sintering the pre-sintered ternary cathode material obtained in the step (5) at a high temperature of 700-900 ℃ for 20-30 hours in an oxygen atmosphere to obtain the nickel-cobalt-manganese ternary cathode material.
Preferably, in the step (1) and the step (3), the nickel salt in the nickel-cobalt-manganese mixed solution is at least one of sulfate, nitrate and chloride, the cobalt salt is at least one of sulfate, nitrate and chloride, the manganese salt is at least one of sulfate, nitrate and chloride, and Ni in the nickel-cobalt-manganese mixed solution2+:(Co2++Mn2+) The molar ratio of (A) to (B) is 2.33 to 7.33: 1.
Preferably, in the step (1), the volume concentration of carbon dioxide in the mixed gas is 10 to 20%, and the molar ratio of carbon dioxide to the sum of cobalt ions and manganese ions is 0.5 to 1: 1.
Preferably, in the step (1), the nickel ion in the nucleus is divalent, and the valence of the cobalt ion and the manganese ion are trivalent, and the general formula is [ Ni2+ 1−x-yCo3+ x Mn3+ y(OH)2]CO3 2- (x+y)/2Wherein, the value of (x + y) is more than or equal to 0.17 and less than or equal to 0.33.
Preferably, in the step (3), the valence states of the nickel ion, the cobalt ion and the manganese ion in the shell are all divalent, and the general formula is Ni2+ 1-x-yCo2+ xMn2+ y(OH)2Wherein, the value of (x + y) is more than or equal to 0.17 and less than or equal to 0.33.
Preferably, in the step (3), the complexing agent is at least one of ammonia water, ammonium sulfate, ammonium nitrate and ammonium chloride, and the content of ammonia in the reaction solution is controlled to be 1-2 mol/L.
Preferably, in the step (1), the stirring speed is 100 to 300 rpm.
Preferably, in the step (3), the stirring speed is 300 to 600 rpm.
Preferably, in the step (1), the step (2), and the step (3), the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution.
The invention has the design characteristics and beneficial effects that: the invention firstly synthesizes a composite alpha and beta type nickel cobalt manganese ternary precursor with a core-shell structure, and then the composite alpha and beta type nickel cobalt manganese ternary precursor is sintered into a ternary anode material. The nickel-cobalt-manganese ternary precursor with the composite alpha and beta core-shell structure is sintered to obtain the nickel-cobalt-manganese ternary cathode material with the inherited structure, because loose alpha-type hydroxide particles are arranged inside the particles and more densely piled beta-type hydroxide is arranged outside the particles. The precursor has better sintering processability, and particularly shows lower residual lithium after sintering. The positive electrode material has better performance than a common positive electrode material, and is particularly characterized in that the capacity of the positive electrode material is good, the capacity retention rate is higher after multiple cycles, and the electrochemical performance is outstanding because more secondary spherical particles have more internal gaps, the lithium ion transition is smoother, and the breakage of crystals caused by anisotropy is reduced.
Drawings
FIG. 1 is an XRD pattern of ternary precursors of examples and comparative examples;
FIG. 2 is a SEM image of a precursor cross section of an example and a comparative example;
FIG. 3 is a graph showing the trend of the cycle capacity of 100 cycles of the examples and comparative examples.
Detailed Description
The invention is further described with reference to the following figures and examples.
Examples
(1) Introducing a mixed gas of carbon dioxide and oxygen into the reaction device, wherein the volume concentration of the carbon dioxide is 15%, and the molar ratio of the carbon dioxide to the cobalt manganese is 0.6: 1; the method comprises the following steps of (1) uniformly starting a 2mol/L nickel-cobalt-manganese mixed solution to feed liquid, wherein the molar coefficient ratio of nickel, cobalt and manganese is 78: 11: 11; simultaneously adding sodium hydroxide solution to control the pH value of the reaction solution to be 10 +/-0.1, intensively stirring in the feeding process at the stirring speed of 200rpm, and preparing an alpha-nickel-cobalt-manganese ternary precursor with the chemical formula of [ Ni ] at the reaction temperature of 80 DEG C2+ 0.78Co3+ 0.11 Mn3+ 0.11(OH)2]CO3 2- 0.11The alpha-type nickel-cobalt-manganese ternary precursor is used as the core of the nickel-cobalt-manganese ternary precursor with a core-shell structure.
(2) And (3) suspending liquid adding, switching the mixed gas to nitrogen, adjusting the temperature of the reaction device to 50 ℃, and adding a sodium hydroxide solution to adjust the pH value of the reaction liquid to 12 after 2 hours of crystallization.
(3) Adding the nickel-cobalt-manganese mixed solution and the 4mol/L ammonium nitrate solution complexing agent solution in the step (1) into the reaction device respectively in a constant-speed parallel-flow mode, wherein the ammonia content of the complexing agent in the reaction liquid is controlled to be 1.5mol/L, simultaneously adding a sodium hydroxide solution to control the pH value of the reaction liquid in the reaction device to be 12 +/-0.1, strongly stirring in the feeding process at the stirring speed of 400rpm, controlling the reaction temperature to be 50 ℃, and reacting under the protection of nitrogen atmosphere to prepare a beta-type nickel-cobalt-manganese ternary precursor with a chemical formula of Ni2+ 0.78Co2+ 0.11Mn2+ 0.11(OH)2The beta type nickel-cobalt-manganese ternary precursor is used as a shell of the nickel-cobalt-manganese ternary precursor with a core-shell structure.
(4) And (4) aging, liquid-solid separation, washing and drying the product obtained in the step (3) to obtain the nickel-cobalt-manganese ternary precursor with the composite alpha and beta type core-shell structure.
(5) And (3) ball-milling and mixing the nickel-cobalt-manganese ternary precursor obtained in the step (4) with lithium hydroxide, wherein the molar ratio of the sum of nickel-cobalt-manganese in the precursor to the lithium hydroxide is 1: 1.05, sintering for 6 hours at 500 ℃ in air atmosphere to obtain the pre-sintered ternary cathode material.
(6) And (4) sintering the pre-sintered ternary cathode material obtained in the step (5) at a high temperature of 800 ℃ for 18 hours in an oxygen atmosphere to obtain the final nickel-cobalt-manganese ternary cathode material.
As can be seen from fig. 1 and fig. 2, the precursor sample prepared in the embodiment has characteristic diffraction peaks of alpha-type and beta-type hydroxides, and after the precursor is roasted by mixing lithium, the obtained nickel-cobalt-manganese ternary positive electrode material has a compact surface and a loose interior, and shows good core-shell structure inheritance.
Comparative example
(1) Adding 2mol/L of nickel-cobalt-manganese mixed nitrate solution and 4mol/L of ammonium nitrate solution into the reaction device respectively in a constant-speed parallel-flow mode, wherein the molar coefficient ratio of nickel-cobalt-manganese is 78: 11: 11, controlling the ammonia content of the complexing agent in the reaction liquid to be 1.5 mol/L; and simultaneously adding a sodium hydroxide solution to control the pH value of the reaction solution in the reaction device to be 12 +/-0.1, strongly stirring in the feeding process at the stirring speed of 400rpm and the reaction temperature of 50 ℃, and reacting under the protection of a nitrogen atmosphere to prepare the beta-type nickel-cobalt-manganese ternary precursor.
(2) Aging, liquid-solid separation, washing and drying the product obtained in the step (1) to obtain a nickel-cobalt-manganese ternary precursor with a composite beta type core-shell structure, wherein the chemical formula is Ni2+ 0.78Co2+ 0.11Mn2+ 0.11(OH)2
(3) And (3) ball-milling and mixing the nickel-cobalt-manganese ternary precursor obtained in the step (2) with lithium hydroxide, wherein the molar ratio of the sum of nickel-cobalt-manganese in the precursor to the lithium hydroxide is 1: 1.05, sintering for 6 hours at 500 ℃ in air atmosphere to obtain the pre-sintered ternary cathode material.
(4) And (4) sintering the pre-sintered ternary cathode material obtained in the step (3) at a high temperature of 800 ℃ for 18 hours in an oxygen atmosphere to obtain the final nickel-cobalt-manganese ternary cathode material.
As can be seen by combining the graphs of FIG. 1 and FIG. 2, the precursor sample prepared by the comparative example has the characteristic diffraction peak of beta-type hydroxide, and after the precursor is mixed with lithium and roasted, the surface and the interior of the obtained nickel-cobalt-manganese ternary positive electrode material are compact.
The high-nickel ternary cathode material obtained in the embodiment and the comparative example is assembled into a button cell, and the method comprises the following specific steps: uniformly mixing the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 94: 3, stirring for 2h, uniformly coating on an aluminum foil, then carrying out vacuum baking at 80 ℃, tabletting, and cutting a positive electrode sheet with the diameter of 14 mm. A button cell is assembled by taking a pure lithium sheet with the diameter of 16mm as a negative electrode sheet, taking a mixed solution of 1mol/L LiPF6+ DEC/EC (volume ratio of 1: 1) as an electrolyte and taking a polypropylene microporous membrane as a diaphragm in a glove box filled with protective gas. And testing the initial discharge specific capacity and 100-cycle capacity retention rate of the button cell by adopting an LAND cell testing system in a voltage range of 2.8-4.35V under the conditions of 25 ℃ and 0.2C charge and discharge, wherein the test data are shown in the following table. And as can be seen from fig. 3, in the examples, the residual lithium content of the sample is low, the capacity retention rate is high after 100 cycles, and the sample shows high electrochemical performance.
Table 1: comparative table of chemical properties of examples and comparative examples
Sample numbering 0.2C first discharge (mAh/g) Capacity retention (%) after 100 cycles Residual lithium content (ppm)
Examples 224 95.99 774
Comparative example 198 90.10 2268
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (8)

1. A preparation method of a nickel-cobalt-manganese ternary cathode material is characterized by comprising the following steps: sequentially comprises the following steps:
introducing mixed gas of carbon dioxide and oxygen into a reaction device, adding a nickel-cobalt-manganese mixed solution into the reaction device at a constant speed, simultaneously adding an alkali solution to control the pH value of a reaction solution in the reaction device to be 9.5-10.5, strongly stirring in a feeding process, and preparing a core of a nickel-cobalt-manganese ternary precursor with a core-shell structure at a reaction temperature of 75-95 ℃, wherein the core is the nickel-cobalt-manganese ternary precursor with an alpha-type structure; in the step (1), the coreThe nickel ion is divalent, the valence states of the cobalt ion and the manganese ion are trivalent, and the general formula of the nucleus is [ Ni ]2+ 1−x-yCo3+ x Mn3+ y(OH)2]CO3 2- (x+y)/2Wherein, x + y is more than or equal to 0.17 and less than or equal to 0.33;
step (2), adding liquid temporarily, switching the mixed gas to nitrogen, adjusting the temperature in the reaction device to 45-65 ℃, and adding an alkali solution to adjust the pH value of the reaction liquid to 11.5-12.5 after crystallization for 1-2 hours;
step (3), adding the nickel-cobalt-manganese mixed solution and the complexing agent solution into the reaction device respectively in a constant-speed parallel flow mode, simultaneously adding an alkali solution to control the pH value of a reaction solution in the reaction device to be 11.5-12.5, strongly stirring in a feeding process, controlling the reaction temperature to be 45-65 ℃, and reacting under the protection of a nitrogen atmosphere to prepare a shell of a nickel-cobalt-manganese ternary precursor with a core-shell structure, wherein the shell is a nickel-cobalt-manganese ternary precursor with a beta-type structure;
step (4), aging, liquid-solid separation, washing and drying the product obtained in the step (3) to obtain a nickel-cobalt-manganese ternary precursor with a composite alpha and beta type core-shell structure;
and (5) ball-milling and mixing the core-shell structure nickel-cobalt-manganese ternary precursor obtained in the step (4) with lithium hydroxide, wherein the molar ratio of the sum of nickel ions, cobalt ions and manganese ions in the core-shell structure nickel-cobalt-manganese ternary precursor to the lithium hydroxide is 1: 1.05, sintering for 6-10 hours at 400-600 ℃ in an air atmosphere to obtain a pre-sintered ternary cathode material;
and (6) sintering the pre-sintered ternary cathode material obtained in the step (5) at a high temperature of 700-900 ℃ for 20-30 hours in an oxygen atmosphere to obtain the nickel-cobalt-manganese ternary cathode material.
2. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (1) and the step (3), the nickel salt in the nickel-cobalt-manganese mixed solution is at least one of sulfate, nitrate and chloride, and the cobalt salt is sulfate and nitrateAnd chloride, manganese salt is at least one of sulfate, nitrate and chloride, and Ni is contained in the mixed solution of nickel, cobalt and manganese2+:(Co2++Mn2+) The molar ratio of (A) to (B) is 2.33 to 7.33: 1.
3. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (1), the volume concentration of carbon dioxide in the mixed gas is 10-20%, and the molar ratio of the carbon dioxide to the sum of cobalt ions and manganese ions is 0.5-1: 1.
4. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (3), the valence states of the nickel ion, the cobalt ion and the manganese ion in the shell are all divalent, and the general formula is Ni2+ 1-x-yCo2+ xMn2+ y(OH)2Wherein, the value of (x + y) is more than or equal to 0.17 and less than or equal to 0.33.
5. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (3), the complexing agent is ammonia water, and the content of ammonia in the reaction solution is controlled to be 1-2 mol/L.
6. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (1), the stirring speed is 100-300 rpm.
7. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (3), the stirring speed is 300-600 rpm.
8. The method for preparing a nickel-cobalt-manganese ternary positive electrode material according to claim 1, characterized in that: in the step (1), the step (2) and the step (3), the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution.
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