CN113571695A - Preparation method of gradient ternary cathode material with coating layer - Google Patents

Preparation method of gradient ternary cathode material with coating layer Download PDF

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CN113571695A
CN113571695A CN202111109999.XA CN202111109999A CN113571695A CN 113571695 A CN113571695 A CN 113571695A CN 202111109999 A CN202111109999 A CN 202111109999A CN 113571695 A CN113571695 A CN 113571695A
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coating layer
lini
ternary cathode
gradient
cathode material
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CN113571695B (en
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宋刘斌
都金莲
肖忠良
李灵均
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Changsha University of Science and Technology
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Abstract

The invention discloses a preparation method of a gradient ternary cathode material with a coating layer. The material is LiNixCoyMnzO2，0.7<x<1, y and z are not 0, x + y + z =1 material is taken as a main body material, and LiNi is taken asxCoyMnzO2，0.5<z<0.6, neither x nor y is 0, x + y + z =1, or LiNixMnzO2，0.5<z<The material with 0.6, x + z =1 is coated by a thin layerA ternary positive electrode material formed on the surface of the host material; the Ni content in the main material is gradually reduced from inside to outside, and the Co and Mn content is gradually increased from inside to outside. The material synthesized by the invention modifies the structure of the traditional pure phase ternary cathode material, and the electrochemical performance of the material is obviously superior to that of the traditional pure phase ternary cathode material. In a word, the modified ternary cathode material for the high-nickel lithium ion battery not only has excellent electrical property, but also has strong safety.

Description

Preparation method of gradient ternary cathode material with coating layer
Technical Field
The invention belongs to the field of preparation of lithium ion battery anode materials. In particular to a preparation method of a gradient high nickel type lithium ion battery ternary anode material with a high manganese thin coating layer.
Background
With the increasing severity of environmental problems, the reduction of the use of fossil fuels becomes a key problem, and lithium ion batteries become a serious problem of energy storage devices nowadays due to the advantages of high energy density, long cycle service life and the like. The nickel-cobalt-manganese (NCM) ternary positive electrode material is concerned because of its high energy density, but the nickel-cobalt ternary material is susceptible to structural defects and side reactions, which affect the electron transfer and lithium ion deintercalation. In order to break through the simple modification means of doping and cladding, the material structure needs to be started, so that the battery performance is improved by optimizing the material structure.
The high nickel ternary material is designed into a gradient material, so that the matching degree with the outermost high manganese thin coating layer can be enhanced. Therefore, the high-capacity performance of the material is maintained, and the structural stability and the thermal stability of the material are improved. And the synthesis method of the material has high repeatability and consistency, and is suitable for large-scale production. The high nickel material accounts for more than half of the total composition of the material, and the extremely high nickel content provides high energy density for the material, but Ni2+With Li+The mixed discharge of cations is easy to occur, and the surface of the high nickel material is easy to generate side reaction with external substances. The + 4-valent Mn with electrochemical inertia can ensure the structural stability at high temperature, and the + 3-valent Co can ensure the conductivity of the material, regulate cation disorder and reduce surface energy. Therefore, a gradual-change type high-nickel material with gradually-reduced Ni content and gradually-increased Co content and Mn content is used as a main body, and a high-manganese material with 2% -7% is used as a coating layer, so that the aim of greatly improving the stability of the material without reducing the energy density of the material is fulfilled.
The ternary cathode material integrating the advantages of the gradual-change type high-nickel material and the high-manganese thin coating layer structurally optimizes the traditional pure-phase high-nickel LNCM ternary cathode material, and improves the energy density, the cycle performance, the rate capability and the safety performance of the material. The simple preparation process also greatly improves the consistency and the repeatability of production, and the gradual change type material with the coating layer can promote the application of the cathode material in the lithium ion battery industry.
Disclosure of Invention
In order to further improve the specific capacity, rate capability, safety performance and stability of the ternary cathode material, the invention mainly aims to provide the ternary cathode material for the lithium ion battery, and the cathode material has good cycle performance, rate capability, safety and stability, and provides a new choice for the lithium ion battery material.
A gradient ternary positive electrode material with a coating layer is LiNixCoyMnzO2，0.7<x<1, y and z are not 0, and x + y + z =1 material is taken as a core and LiNi is taken asxCoyMnzO2，0.5<z<0.6, neither x nor y is 0, x + y + z =1, or LiNixMnzO2，0.5<z<0.6, wherein the material with x + z =1 is a ternary cathode material formed by coating a thin layer on the surface of a main material; the Ni content in the main material is gradually reduced from inside to outside, and the Co and Mn content is gradually increased from inside to outside.
Further, the particle size is 4-10 mu m.
Still further, the mass percentage of the main material is not less than 90%.
The second purpose of the invention is to provide a preparation method of the above gradient ternary cathode material with a coating layer, which comprises the following steps:
(1) to form LiNi after calcinationxCoyMnzO2，0.7<x<1, y and z are not 0, Ni, Co and Mn sources required by the material x + y + z =1 are used as aqueous solution prepared by raw materials, a coprecipitation method is adopted, and the pH value of the system is uniformly increased from 10.5-11.5 in the reaction process to obtain a precursor of the gradual change type main body material;
(2) to form LiNi after calcinationxCoyMnzO2，0.5<z<0.6, x and y are allNot 0, x + y + z =1, or LiNixMnzO2，0.5<z<0.6, x + z =1 Ni required for the material、Co、Adding an aqueous solution prepared by taking a Mn source as a raw material into the gradient type main body material obtained in the step (1), and fixing a pH value within the range of 10-12 by adopting a coprecipitation method to react to obtain a precursor of the gradient type ternary cathode material with a coating layer;
(3) mixing the precursor obtained in the step (2) with a lithium source in proportion, and grinding; and carrying out high-temperature calcination.
The above process, steps (1) and (2) are carried out with NH3·H2O is taken as a complexing agent, and sodium hydroxide or potassium hydroxide aqueous solution is taken as a pH control agent; the reaction temperature is 50-65 ℃, and the stirring speed is 600-1000 r/min.
In the method, the high-temperature calcination temperature in the step (3) is 780-800 ℃, and the heat preservation time is 10-15 h. The temperature rise rate during calcination is 3-5 ℃/min.
Cation diffusion occurs during high temperature calcination, and the diffusion rate is directly related to the element content and the reaction temperature. Under 800 ℃, the cation diffusion is small, under 800-850 ℃, the cation diffusion is moderate, and under 850 ℃, the cation diffusion is severe. To convert cation (Ni)2+、Co3+、Mn4+) Diffusion occurs between the graded material and the coating layer, and the calcination temperature should be controlled between 780 and 800 ℃.
In the above method, the lithium source is: one or more of lithium hydroxide, lithium carbonate and lithium oxalate; ni、Co、The source of Mn is NiSO respectively4、CoSO4、MnSO4Or a crystalline hydrate compound thereof.
In the method, the steps (1) and (2) are carried out in a nitrogen atmosphere or an inert atmosphere, and the atmosphere in the high-temperature calcination of the step (3) is O2And air.
The third purpose of the invention is to provide the application of the above-mentioned gradient ternary cathode material with a thin coating layer, which is used for preparing the cathode material of a lithium ion battery.
The nuclear material of the invention is a high nickel material, which accounts for more than 90 percent of the total composition of the material, and the extremely high nickel content provides high energy density for the material, but Ni2+With Li+Cation mixing and discharging are easy to occur; and the surface of the high nickel material is easy to react to generate a lithium-containing compound. Therefore, the electrochemical inert + 4-valent Mn (ensuring the structural stability at high temperature) and + 3-valent Co (ensuring the conductivity of the material, adjusting the cation disorder and reducing the surface energy) are also required to be added. The nickel-rich material with a special structure is formed by taking a gradual-change type nickel-rich material with the Ni content gradually reduced from inside to outside and the Co and Mn content gradually increased from inside to outside as a main body and taking a high-manganese material with the content of 2% -7% as a coating layer, so that the aim of greatly improving the stability of the material without reducing the energy density of the material is fulfilled.
The invention has the advantages of
(1) The invention takes the gradual change type nickelic ternary anode material as the main material, which accounts for more than 90 percent of the total composition of the material. The high-nickel material ensures that the material has high energy density, and the gradual change structure can ensure that the matching degree of the main body material and the high-manganese coating layer is higher, thereby preventing the problem of structural cracking caused by large component difference between the coating layer and the main body material in a high-temperature and high-pressure environment.
(2) The material of the invention adopts the high manganese anode material as the thin coating layer for the first time, and the coating layer can greatly improve the stability of the material without reducing the energy density of the material. The coating layer and the main material are both materials consisting of Ni, Co and Mn, and different from the prior non-battery material coating, a dissolving system is not required to be found in the coating process, and after the coprecipitation reaction of the main material is finished, the coprecipitation reaction is continued to coat the main material.
Drawings
FIG. 1: FIB pictures of cross sections of the precursors prepared in example 1.
FIG. 2: example 1 the precursor cross section was prepared with the selected EDS line scan location.
FIG. 3: EDS line scan spectra of Ni, Co and Mn on the cross section of the precursor prepared in example 1.
FIG. 4: the EDS line scan spectrum of Mn across the plane of the precursor prepared in example 1.
FIG. 5: the EDS line scan spectrum of Ni across the street for the precursor prepared in example 1.
FIG. 6: the EDS line scan spectrum of Co across the street for the precursor prepared in example 1.
FIG. 7: XRD pattern of the cathode material prepared in example 1.
FIG. 8: XRD pictures of the cathode material prepared in comparative example 1.
FIG. 9: the cathode material prepared in example 1 and SEM pictures thereof before 100 cycles of 2.7-4.3V, 1C.
FIG. 10: the cathode material prepared in example 1 and SEM pictures thereof after 100 cycles of 2.7-4.3V, 1C.
FIG. 11: the cathode material prepared in comparative example 1 and SEM pictures thereof before 100 cycles of 2.7-4.3V, 1C.
FIG. 12: the cathode material prepared in comparative example 1 and SEM pictures thereof after 100 cycles of 2.7-4.3V, 1C.
FIG. 13: the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3, 4, 5 and 6 have 100 cycles of electrical property diagrams at 2.7-4.3V and 1C.
FIG. 14: cycling performance plots of the positive electrode materials prepared in examples 1 and 2 and comparative examples 1, 2, 3, 4, 5 and 6 at different rates.
Detailed Description
The present invention is described in further detail below with reference to examples, but the scope of the present invention is not limited thereto.
In the embodiment, a ternary cathode material of a gradient high-nickel lithium ion battery with a high-manganese thin coating layer is synthesized, wherein: LiNi as host material0.9Co0.05Mn0.05O2Or LiNi0.7Co0.2Mn0.1O2High manganese LiNi accounting for 97 percent of the total composition of the material0.3Co0.2Mn0.5O2Or LiNi0.4Mn0.6O2The coating layer is only 3% of the total material composition.
Example 1
And synthesizing the gradient high-nickel ternary cathode material with the high-manganese thin coating layer by adopting a coprecipitation method. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2776ml of aqueous solution of O metal sulfate for use as host material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). In the process of coprecipitation reaction, pH value controlled by sodium hydroxide aqueous solution is changed at constant speed and gradually increased from 10.5 to 11.5; thereby obtaining (Ni) having a graded structure0.9Co0.05Mn0.05(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Co: Mn =3:2:54 ·6H2O、CoSO4·7H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 24mL of O metal sulfate aqueous solution (high manganese thin coating layer solution), controlling the pH value to be 11, and controlling the complexing agent and the pH control agent at the same precipitation temperature and stirring speed. Washing the precipitate with deionized water to neutrality, and air-blast drying at 80 deg.c overnight to obtain the precursor of the gradient type high nickel ternary material with high manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Example 2
And synthesizing the gradient high-nickel ternary cathode material with the high-manganese thin coating layer by adopting a coprecipitation method. Firstly, metal is first put intoNiSO with total ion concentration of 1M and cation ratio of Ni to Co to Mn = 7 to 2 to 14 ·6H2O、CoSO4·7H2O、MnSO4·H2O Metal sulfate aqueous solution 776mL, for use in host Material (Ni)0.7Co0.2Mn0.1(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). In the process of coprecipitation reaction, pH value controlled by sodium hydroxide aqueous solution is changed at constant speed and gradually increased from 10.5 to 11.5; thereby obtaining (Ni) having a graded structure0.7Co0.2Mn0.1(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Mn = 4:64 ·6H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 24mL of O metal sulfate aqueous solution (high manganese thin coating layer solution), controlling the pH value to be 11, and controlling the complexing agent and the pH control agent at the same precipitation temperature and stirring speed. Washing the precipitate with deionized water to neutrality, and air-blast drying at 80 deg.c overnight to obtain the precursor of the gradient type high nickel ternary material with high manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 1 (pure phase)
Synthesis of homogeneous Li (Ni) by coprecipitation method0.882Co0.0545Mn0.0635)O2And (3) a positive electrode material. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 8.82 to 0.545 to 0.635 is prepared4 ·6H2O、CoSO4·7H2O、MnSO4·H2800mL of aqueous O metal sulfate solution. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). Controlling the pH value in the reaction process to be a fixed value: 11.2. the precipitate was washed to neutrality with deionized water and air-dried at 80 ℃ overnight to give a pure phase ((Ni)0.882Co0.0545Mn0.0635)OH2) A precursor material. The precursor is reacted with LiOH. H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 780 ℃ at the speed of 5 ℃/min in the oxygen atmosphere, and calcining at high temperature for 15h to obtain homogeneous Li (Ni)0.882Co0.0545Mn0.0635)O2And (3) a positive electrode material.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 2 (gradation body)
And synthesizing the gradient type high nickel ternary cathode material by adopting a coprecipitation method. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2800mL of O metal sulfate aqueous solution for host material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). During the coprecipitation reaction, the pH value controlled by sodium hydroxide aqueous solution is changed at a constant speed and gradually increased from 10.5 to 11.5. Washing the precipitate with deionized water to neutrality, and air-drying at 80 deg.C overnight to obtain gradient form of (Ni)0.9Co0.05Mn0.05(OH)2) A precursor material. Finally, willDried precursor with LiOH. H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 3 (homogeneous addition coating)
And synthesizing the high-nickel ternary cathode material with the high-manganese thin coating layer by adopting a coprecipitation method. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2O Metal sulfate aqueous solution 776mL, for use in host Material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). In the process of coprecipitation reaction, the pH value controlled by sodium hydroxide aqueous solution is fixed at 11.2; obtaining homogeneous (Ni)0.9Co0.05Mn0.05(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Co: Mn =3:2:54 ·6H2O、CoSO4·7H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 24mL of O metal sulfate aqueous solution (high manganese thin coating layer solution), controlling the pH value to be 11, and controlling the complexing agent and the pH control agent at the same precipitation temperature and stirring speed. And washing the precipitate with deionized water to neutrality, and drying by air blowing at 80 ℃ overnight to obtain the precursor of the high-nickel ternary material with the high-manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 4 (900 ℃ C. sintering)
And synthesizing the gradient high-nickel ternary cathode material with the high-manganese thin coating layer by adopting a coprecipitation method. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2O Metal sulfate aqueous solution 776mL, and its application to host Material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). In the process of coprecipitation reaction, sodium hydroxide solution is used for controlling pH value to be between 10.5 and 11.5 and increasing and changing rapidly at a constant speed; thereby obtaining (Ni) having a graded structure0.9Co0.05Mn0.05(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Co: Mn =3:2:54 ·6H2O、CoSO4·7H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 24mL of O metal sulfate aqueous solution (high manganese thin coating layer solution), controlling the pH value to be 11, and controlling the complexing agent and the pH control agent at the same precipitation temperature and stirring speed. And then washing the precipitate to be neutral by using deionized water, and carrying out forced air drying at 80 ℃ overnight to obtain the precursor of the gradient type high-nickel ternary material with the high-manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 900 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 5 (gradient unevenness)
Adopting a coprecipitation method to synthesize the non-gradual change type high nickel type ternary anode material with the high manganese thin coating layer. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2O in 776mL of an aqueous solution of a metal sulfate, used for the host material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). During the coprecipitation reaction, the pH was controlled to 10.5 and 11.5 using an aqueous solution of sodium hydroxide (pH was controlled to 10.5 using a 50% by volume solution; pH was controlled to 11.5 by adding a 50% by volume solution). Thereby obtaining (Ni) having no graded structure0.9Co0.05Mn0.05(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Co: Mn =3:2:54 ·6H2O、CoSO4·7H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 24mL of metal sulfate aqueous solution (high-manganese thin coating layer solution) of O, controlling the pH value to be 11, and controlling the complexing agent and the pH control agent at the same precipitation temperature and stirring speed. Washing the precipitate with deionized water to neutrality, and air-blast drying at 80 deg.c overnight to obtain the precursor of the non-gradual change type high nickel ternary material with high manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Comparative example 6 (coating thickness 15%)
Adopting a coprecipitation method to synthesize a gradient type high-nickel ternary cathode material with a high-manganese coating layer, wherein: LiNi as host material0.9Co0.05Mn0.05O2High manganese LiNi accounting for 80 percent of the total composition of the material0.3Co0.2Mn0.5O2The coating layer was 20% of the total composition of the material. Firstly, NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni to Co to Mn = 9 to 0.54 ·6H2O、CoSO4·7H2O、MnSO4·H2680mL of an aqueous solution of O in metal sulfate, for use as a host material (Ni)0.9Co0.05Mn0.05(OH)2) And (4) preparing. The reaction is carried out in nitrogen atmosphere, the prepared solution is continuously pumped into a stirring reaction kettle, and the complexing agent is 0.4M NH3·H2O, pH control agent is 4M aqueous sodium hydroxide solution, precipitation temperature (50 ℃), stirring speed (600 rpm). In the process of coprecipitation reaction, sodium hydroxide aqueous solution is used for controlling pH value to be between 10.5 and 11.5 and gradually changing at a constant speed; thereby obtaining (Ni) having a graded structure0.9Co0.05Mn0.05(OH)2) A host material. Then, the obtained host material and NiSO with the total concentration of metal ions of 1M and the cation ratio of Ni: Co: Mn =3:2:54 ·6H2O、CoSO4·7H2O、MnSO4·H2And (3) carrying out coprecipitation reaction on 120mL of metal sulfate aqueous solution (high manganese coating layer solution) of O, controlling the pH value to be 11, and keeping other reaction conditions unchanged. Washing the precipitate with deionized water to neutrality, and blast drying at 80 deg.c overnight to obtain the precursor of the gradient type high nickel ternary material with high manganese thin coating layer. Finally, the dried precursor is reacted with LiOH H2Mixing O according to the molar ratio of 1:1.05, fully grinding, heating to 800 ℃ at the speed of 5 ℃/min in an oxygen atmosphere, and calcining at high temperature for 12 h.
The final product obtained was as active substance: acetylene black: PVDF =8:1:1, mixing and grinding uniformly, adding a proper amount of organic solvent NMP to prepare slurry, uniformly coating the slurry on a 0.02mm aluminum foil, and drying the aluminum foil in a vacuum drying oven at 100 ℃ for 8 hours to prepare a positive plate with the diameter of 14 mm.
Finally, the positive plate obtained in the above examples and comparative examples is used as a positive electrode, the negative electrode is a metal lithium plate, the separator is a microporous polypropylene film (Celgard 2300), and the electrolyte is 1mol/L LiPF6The solution was mixed with/EC + DMC + EMC (volume ratio 1:1: 1). And assembling the positive electrode shell, the positive plate, the diaphragm, the lithium plate, the nickel screen and the negative electrode shell into the button cell in an argon-protected glove box. And standing the assembled battery for 12 hours at room temperature, and then testing the electrochemical performance of the battery by adopting a Wuhan blue electric testing system.
The test result shows that: the cross section of the precursor of the gradient type high-nickel ternary material with the high-manganese thin coating layer obtained by the embodiment of the invention is shown in figure 1, EDS (electro-deposition) line scanning is carried out on the cross section, and the Ni content in the center of the particle is very high and the edge becomes low from the center of the particle to the shell of the particle due to the concentration of Ni, Co and Mn elements; the Mn content in the center of the particles is low, the edge of the particles is obviously high, and the particles have a gradual change trend, and the gradual change type high nickel ternary material precursor with the high manganese thin coating layer is shown in the figures 2-6. From the XRD patterns (FIGS. 7-8) and unit cell parameters of the two positive electrode materials, Li of comparative example 1 was found+/Ni2+The degree of miscellany was 4.12%, which is significantly higher than that of example 1 (degree of miscellany was 3.19%), and table 1 shows that the method of the present invention is effective in reducing Li+/Ni2+And (4) mixing and discharging. As can be seen from the SEM images of fig. 9 to 12, the retention effect of the spherical particles was better in example 1 than in comparative example 1 after the same conditions were cycled 100 times. FIG. 13 shows that the capacity retention of examples 1 and 2 after 2.7-4.3V, 1C and 100 cycles is significantly better than that of comparative examples 1, 2, 3, 4, 5 and 6; figure 14, examples 1, 2 have better magnification performance than comparative examples 1, 2, 3, 4, 5, 6 at different magnification cycles.
Table 1: cell parameters of the positive electrode materials prepared in example 1 and comparative example 1
Sample (I) a(Å) c(Å) c/a V(Å3) Li+/Ni2+Degree of mixing and arrangement
CC-NCM 2.8712 14.1990 4.9453 101.37 4.12%
CG-NCM 2.8691 14.1941 4.9472 101.19 3.19%

Claims (8)

1. The preparation method of the gradient ternary cathode material with the coating layer is characterized in that the gradient ternary cathode material with the coating layer is LiNixCoyMnzO2，0.7<x<1, y and z are not 0, and the material with x + y + z =1 is a gradual change type host material and takes LiNixCoyMnzO2，0.5<z<0.6, neither x nor y is 0, x + y + z =1, or LiNixMnzO2，0.5<z<0.6, wherein the material with x + z =1 is a ternary cathode material formed by coating a thin layer on the surface of a gradual change type main body material; the Ni content in the gradual change type main body material is gradually reduced from inside to outside, and the Co content and the Mn content are gradually increased from inside to outside; the gradient ternary cathode material with the coating layer comprises the following steps:
(1) to form LiNi after calcinationxCoyMnzO2，0.7<x<1, y and z are not 0, Ni, Co and Mn sources required by the material x + y + z =1 are used as aqueous solution prepared by raw materials, a coprecipitation method is adopted, and the pH value of the system is uniformly increased from 10.5 to 11.5 in the reaction process to obtain a precursor of the gradual change type main body material;
(2) to form LiNi after calcinationxCoyMnzO2，0.5<z<0.6, neither x nor y is 0, x + y + z =1, or LiNixMnzO2，0.5<z<0.6, x + z =1 Ni required for the material、Co、Adding an aqueous solution prepared by taking a Mn source as a raw material into the gradient type main body material obtained in the step (1), and fixing a pH value within the range of 10-12 by adopting a coprecipitation method to react to obtain a precursor of the gradient type ternary cathode material with a coating layer;
(3) mixing the precursor obtained in the step (2) with a lithium source in proportion, and grinding; and carrying out high-temperature calcination.
2. The production method according to claim 1, characterized in that the particle size is 4-10 μm.
3. The method of claim 1, wherein the graded host material is not less than 90% by mass.
4. The method of claim 1, wherein steps (1) and (2) are performed using NH3·H2O as complexing agent, sodium hydroxide or oxyhydrogenPotassium dissolving water solution is used as a pH control agent; the reaction temperature is 50-65 ℃, and the stirring speed is 600-1000 r/min.
5. The preparation method according to claim 1, wherein the high temperature calcination temperature in step (3) is 780-800 ℃, and the holding time is 10-15 h.
6. The method of claim 1, wherein the graded host material is not less than 90% by mass.
7. The method of claim 1, wherein the lithium source is: one or more of lithium hydroxide, lithium carbonate and lithium oxalate; the sources of Ni, Co and Mn are respectively NiSO4、CoSO4、MnSO4Or a crystalline hydrate compound thereof.
8. The method according to claim 1, wherein the steps (1) and (2) are carried out in a nitrogen atmosphere or an inert atmosphere, and the atmosphere in the high-temperature calcination of the step (3) is O2And air.
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