CN107403913B - Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof - Google Patents
Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN107403913B CN107403913B CN201710561502.5A CN201710561502A CN107403913B CN 107403913 B CN107403913 B CN 107403913B CN 201710561502 A CN201710561502 A CN 201710561502A CN 107403913 B CN107403913 B CN 107403913B
- Authority
- CN
- China
- Prior art keywords
- boron
- cathode material
- precursor
- temperature
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a surface-modified nickel cobalt lithium aluminate anode material and a preparation method thereof, wherein the anode material consists of a layered material nickel cobalt lithium aluminate anode active substance and a surface modification layer thereof, and the surface modification layer comprises a surface doping modification layer and a boron-containing oxide molten coating layer; the preparation method comprises the following steps: and mixing the boron-containing compound and the ternary precursor by a wet method to obtain a surface pre-coated ternary cathode material precursor, mixing the surface pre-coated ternary cathode material precursor with a lithium salt, and calcining at a high temperature and cooling to obtain the surface modified nickel-cobalt lithium aluminate cathode material. The surface-modified nickel-cobalt lithium aluminate cathode material has the advantages of stable crystal structure, good electrochemical performance, simple process, low energy consumption and cost, and is beneficial to large-scale production of the cathode material.
Description
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a surface-modified nickel cobalt lithium aluminate anode material and a preparation method thereof.
Background
Lithium ion batteries have the advantages of high energy density, high energy efficiency, no memory effect, low self-discharge rate and the like, and have been widely applied to the related fields of consumer electronics products, electric vehicles, large-scale energy storage power stations, aerospace and the like. However, with the rapid development of the current electric vehicles, higher requirements are put on the energy density and the power density of the lithium ion battery, and therefore, a positive electrode material with higher energy density is urgently needed to be found to replace the existing material.
The high-nickel ternary cathode material such as nickel cobalt lithium aluminate cathode material has the advantages of high energy density, low cost and environmental friendliness, thus receiving wide attention of people and being considered as a cathode material with great prospect for lithium ion batteries for electric vehicles. However, as a nickel-based NCA ternary positive electrode material, there are the following problems: firstly, repeated volume change of the anode material in the charge-discharge process easily causes generation of active particle microcracks and polarization increase; secondly, the surface of the material is easy to react with moisture and carbon dioxide in the air to generate LiOH and Li2CO3And the like, which lead to the increase of the surface alkalinity of the material and the change of the surface crystal structure; third, Ni in charged state4+Oxidizing the electrolyte to produce a thicker SEI film and oxygen evolution; fourthly, HF in the electrolyte attacks the surface of the material to dissolve metal ions. The above problems all result in the reduction of electrochemical performance of the ternary cathode material and limit further application thereof.
Research has shown that surface coating of materials is an effective means to solve the above problems. Common surface coating materials include: metal oxides, metal phosphates, fluorides or other positive electrode materials, and the like. However, the currently common surface coating method is a two-step process. Namely: the ternary cathode material prepared by calcination is used as a matrix, and in order to ensure the uniformity of material coating and good electrochemical performance, wet chemical coating needs to be carried out under the condition of an organic solvent such as ethanol, and in addition, secondary calcination is needed to finally obtain the coating modified ternary cathode material. Although the coating method can obtain better electrochemical performance under laboratory conditions, the increase of the process flow and the harsh preparation conditions can cause the increase of the production cost, and the complex operation process is not beneficial to the large-scale production in industry.
Disclosure of Invention
In view of the above, the present application provides a surface-modified nickel-cobalt lithium aluminate positive electrode material and a preparation method thereof, the obtained positive electrode material has a stable crystal structure, surface side reactions are inhibited, electrochemical performance is significantly improved, the preparation by a pre-coating method can be realized, the process is simple, secondary surface modification is not required, energy consumption and production cost are reduced, and thus, the large-scale production and application are facilitated.
In order to solve the technical problems, the technical scheme provided by the invention is a surface-modified nickel cobalt lithium aluminate anode material, the anode material consists of a layered material nickel cobalt lithium aluminate anode active substance and a surface modification layer, and the surface modification layer comprises a surface doping modification layer and a boron-containing oxide molten coating layer.
Preferably, the chemical formula of the cathode material is LiNixCoyAlzO2Wherein x + y + z is 1, and x is not less than 0.5<0.9，0<y≤0.3，0<z≤0.1。
Preferably, the positive electrode material is spherical or spheroidal particle, and the particle size range of the particle is 0.5-20 um.
Preferably, in the boron-containing oxide molten coating layer, the molar ratio of the boron element to the positive electrode material is (0.1-5): 100.
The technical scheme of the application also provides a preparation method of the surface-modified nickel cobalt lithium aluminate anode material, which comprises the following steps:
(1) mixing a boron-containing compound with NixCoyAlz(OH)2The ternary precursor is mixed by a wet method to obtain a surface pre-coated ternary cathode material precursor;
(2) and mixing the precursor of the ternary cathode material with the pre-coated surface with lithium salt, calcining at high temperature, and cooling to obtain the surface-modified nickel-cobalt lithium aluminate cathode material.
Wherein the boron-containing compound has a chemical formula of NixCoyAlz(OH)2The molar ratio of the ternary precursor of (a) is 1: (49-99).
Preferably, the boron-containing compound in step (1) is at least one of ammonium borate, boric acid, diboron trioxide and lithium metaborate.
Preferably, the chemical formula in step (1) is NixCoyAlz(OH)2In the ternary precursor, the nickel content is not less than 60 percent, and x is not less than 0.5<0.9，0<y≤0.3，0<z≤0.1。
Preferably, the lithium salt in step (2) is at least one of lithium hydroxide or lithium carbonate.
Preferably, the wet mixing in step (1) is specifically: and mixing the weighed ternary precursor with a boron-containing compound, adding deionized water to obtain a mixed aqueous solution, dissolving for 0.5-2 hours at the temperature of 30-60 ℃ under stirring, heating to 70-100 ℃, continuing stirring for 3-8 hours until water is completely evaporated, and performing vacuum drying for 3-12 hours at the temperature of 80-120 ℃ to obtain the surface pre-coated ternary cathode material precursor.
More preferably, the total mass of the ternary precursor and the boron-containing compound is 20-50% of the mass of the mixed aqueous solution.
Preferably, the high-temperature calcination in the step (2) comprises a first constant-temperature stage and a second constant-temperature stage, wherein the first constant-temperature stage is 300-500 ℃, the second constant-temperature stage is 720-800 ℃, and the time of the first constant-temperature stage and the time of the second constant-temperature stage are both 0.5-15 hours.
Preferably, in the high-temperature calcination and cooling process in the step (2), the temperature rise rate is controlled to be 2-20 ℃/min, and the temperature reduction rate is controlled to be 0.1 ℃/min for furnace cooling.
According to the technical scheme, the nickel cobalt lithium aluminate anode material is obtained by surface modification in the processes of precursor preparation and high-temperature calcination, wherein in the high-temperature calcination, boron in a boron-containing compound is doped into a crystal lattice phase of the anode material at a high temperature and is coordinated with oxygen atoms in the crystal lattice to form boric acid polyanion, and a transition phase is formed, so that the surface modification part and a main material part are combined more tightly, the crystal lattice stability and the thermal stability are improved, the release of oxygen in the anode material is hindered, the safety performance is improved, and the electrochemical performance of the anode material can be obviously improved.
In addition, the technical scheme of the application adopts a method of pre-coating the precursor, and then subsequent high-temperature calcination is carried out to obtain the high-quality surface-modified nickel-cobalt lithium aluminate cathode material, so that the process flow is simplified, compared with the traditional two-step coating, the process conditions and the operation steps are simpler, the production conditions are milder and easier to control, no organic solvent is needed in the preparation process, no pollution is caused, the production cost is saved, and the large-scale production application is facilitated.
Based on the above explanation, this application technical scheme lies in for prior art, its beneficial effect:
(1) the selected boron-containing compound can be uniformly deposited on the ternary precursor to obtain a ternary anode material precursor with a pre-coated surface, the nickel-cobalt lithium aluminate anode material modified by the boric acid polyanion surface is prepared by high-temperature calcination, partial boron atoms of the surface modification layer are doped into a crystal lattice phase of the anode material under the high-temperature treatment condition and are coordinated with oxygen to form the boric acid polyanion, the crystal structure is stabilized, the surface side reaction is inhibited, and a layer of transition phase is formed, so that the surface modification layer is combined with the main body material more tightly, the electrochemical performance is remarkably improved, the release of oxygen in the anode material is hindered, and the safety performance is improved.
(2) Compared with the traditional two-step coating method, the pre-coating method has the advantages that the process conditions and the operation steps are simpler, secondary surface modification is not needed, the production conditions are mild and easy to control, an organic solvent is not needed in the preparation process, no pollution is caused, the production cost is saved, and the large-scale production and application are facilitated.
(3) The surface-modified nickel-cobalt lithium aluminate cathode material prepared by the method provided by the invention has good thermal stability and excellent cycle performance.
Drawings
Fig. 1 is an SEM image of a ternary positive electrode material precursor without surface modification in example 1 of the present application;
fig. 2 is an SEM image of the surface-modified ternary positive electrode material precursor in example 1 of the present application;
FIG. 3 is an SEM image of a surface-modified lithium nickel cobalt aluminate positive electrode material in example 1 of the present application;
FIG. 4 is an SEM image of a surface-modified lithium nickel cobalt aluminate positive electrode material in example 2 of the present application;
fig. 5 is an XRD pattern of the surface-modified lithium nickel cobalt aluminate positive electrode material in example 2 of the present application.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
The technical scheme of this application a nickel cobalt lithium aluminate cathode material of surface modification constitute by layered material nickel cobalt lithium aluminate cathode active material rather than the modification modified layer on surface, the surface modification modified layer includes surface doping modified layer and boron oxide containing melt coating layer. The lithium ion battery is prepared by mixing a ternary positive electrode material precursor pre-coated on the surface of a boron-containing compound with lithium salt and calcining at high temperature. In the surface-modified nickel cobalt lithium aluminate anode material, the molar ratio of boron to the anode material is (0.1-5): 100. The positive electrode material is spherical or spheroidal particles, the particle size is 0.5-20 um, and specifically, the nickel-cobalt lithium aluminate particles with the surface modified are spherical or spheroidal, and the particle size is 0.5-20 um. The chemical formula of the anode material is LiNixCoyAlzO2Wherein x + y + z is 1, and x is not less than 0.5<0.9，0<y≤0.3，0<z≤0.1。
The preparation method comprises the following steps of mixing the boron-containing compound with NixCoyAlz(OH)2The ternary precursor is mixed by a wet method to obtain a surface pre-coated ternary cathode material precursor; and mixing the precursor of the ternary cathode material with the pre-coated surface with lithium salt, calcining at high temperature, and cooling to obtain the surface-modified nickel-cobalt lithium aluminate cathode material.
Wherein the boron-containing compound is at least one of ammonium borate, boric acid, diboron trioxide and lithium metaborate.
Wherein the wet mixing specifically comprises: and mixing the weighed ternary precursor with a boron-containing compound, adding deionized water to obtain a mixed aqueous solution, dissolving for 0.5-2 hours at the temperature of 30-60 ℃ under stirring, heating to 70-100 ℃, continuing stirring for 3-8 hours until water is completely evaporated, and performing vacuum drying for 3-12 hours at the temperature of 80-120 ℃ to obtain the surface pre-coated ternary cathode material precursor.
The high-temperature calcination comprises a first constant-temperature stage and a second constant-temperature stage, wherein the first constant-temperature stage is 300-500 ℃, the second constant-temperature stage is 720-800 ℃, and the time of the first constant-temperature stage and the time of the second constant-temperature stage are both 0.5-15 hours; and in the high-temperature calcination and cooling process, controlling the heating rate to be 2-20 ℃/min and the cooling rate to be 0.1 ℃/min to cool along with the furnace.
The lithium nickel cobalt aluminate cathode material with the surface modified by the polyanion borate surface, which is prepared by mixing the surface pre-coated ternary cathode material precursor with lithium salt and calcining at high temperature, has good thermal stability and excellent cycle performance.
The technical effect of the technology of the present application is verified by combining the parameter settings and the experimental results in the specific embodiments and by combining the drawings.
Example 1
Boric acid as boron-containing compound and ternary precursor mixed metal hydroxide Ni0.8Co0.15Al0.05(OH)2(the SEM picture is shown in figure 1) is subjected to surface pre-coating, and then the surface modified nickel cobalt lithium aluminate anode material is prepared by high-temperature calcination, and the preparation method comprises the following steps:
(1) preparation of surface pre-coated ternary cathode material precursor
Adding the ternary precursor mixed metal hydroxide and boric acid into a beaker according to the molar ratio of 98:2, adding a certain amount of deionized water into the beaker, wherein the total content of the mixed metal hydroxide and the boric acid is 30%, stirring and dissolving the mixture for 2 hours at 40 ℃, and then heating to 80 ℃ and continuing stirring until the water is completely evaporated. And transferring the obtained mixture into an oven, and carrying out vacuum drying for 5h at 120 ℃ to obtain the ternary cathode material precursor pre-coated on the surface of boric acid. The SEM image is shown in FIG. 2.
(2) Preparation of surface modified nickel cobalt lithium aluminate anode material
And (3) mixing the obtained precursor of the surface pre-coated ternary cathode material with LiOH according to the mol ratio of 1: 1.05 weighing, fully mixing and grinding, transferring the mixed powder into a corundum boat after grinding uniformly, and pushingCalcining in the center of the tube furnace while introducing oxygen. The heating rate is 5 ℃/min, the reaction is firstly carried out for 5h under the temperature of 450 ℃, then the temperature is raised to 720 ℃ and the sintering is carried out for 15h, the nickel-cobalt lithium aluminate anode material with modified surface is obtained, and the first-circle specific discharge capacity is 185.9mAh g through the electrochemical performance test-1. The solution is circulated for 200 circles under the magnification of 2C, and the capacity retention rate is 97.2 percent.
Example 2
Ternary precursor mixed metal hydroxide Ni with ammonium borate as boron-containing compound0.8Co0.15Al0.05(OH)2After surface pre-coating, the surface modified nickel cobalt lithium aluminate anode material is prepared by high-temperature calcination, and the preparation method comprises the following steps:
(1) preparation of surface pre-coated ternary cathode material precursor
Adding the ternary precursor mixed metal hydroxide and ammonium borate into a beaker according to the molar ratio of 99:1, adding a certain amount of deionized water into the beaker, wherein the total content of the mixed metal hydroxide and the ammonium borate is 20%, stirring and dissolving the mixture for 1 hour at 30 ℃, and then heating the mixture to 90 ℃ and continuing stirring until the water is completely evaporated. And transferring the obtained mixture into an oven, and carrying out vacuum drying for 12h at 100 ℃ to obtain the precursor of the ternary cathode material pre-coated on the surface of ammonium borate.
(2) Preparation of surface modified nickel cobalt lithium aluminate anode material
And (3) mixing the obtained surface pre-coated ternary positive electrode material precursor with lithium carbonate according to the molar ratio of 1: 1.05, fully mixing and grinding, transferring the mixed powder into a corundum boat after grinding uniformly, pushing the corundum boat to the center of a tube furnace for calcining, and introducing oxygen. The heating rate is 2 ℃/min, the reaction is firstly carried out for 5h under the temperature of 450 ℃, then the temperature is increased to 800 ℃ and the sintering is carried out for 15h, the nickel cobalt lithium aluminate anode material with the modified surface is obtained (an SEM picture is shown in figure 4, an XRD picture is shown in figure 5), and the specific discharge capacity of the first circle is 189.6mAh g through electrochemical performance test-1. The solution is circulated for 200 circles under the magnification of 2C, and the capacity retention rate is 88.7 percent.
Example 3
Boron trioxide containing boronCompound-to-ternary precursor mixed metal hydroxide Ni0.8Co0.15Al0.05(OH)2After surface pre-coating, the surface modified nickel cobalt lithium aluminate anode material is prepared by high-temperature calcination, and the preparation method comprises the following steps:
(1) preparation of surface pre-coated ternary cathode material precursor
Adding the ternary precursor mixed metal hydroxide and boron trioxide into a beaker according to the molar ratio of 98:2, adding a certain amount of deionized water into the beaker, wherein the total content of the mixed metal hydroxide and the boron trioxide is 40%, stirring and dissolving the mixture for 0.5h at 50 ℃, then heating to 70 ℃, and continuing stirring until the water is completely evaporated. And transferring the obtained mixture into an oven, and carrying out vacuum drying for 10h at the temperature of 80 ℃ to obtain the ternary cathode material precursor pre-coated on the surface of the diboron trioxide.
(2) Preparation of surface modified nickel cobalt lithium aluminate anode material
And (3) mixing the obtained surface pre-coated ternary positive electrode material precursor with lithium carbonate according to the molar ratio of 1: 1.05, fully mixing and grinding, transferring the mixed powder into a corundum boat after grinding uniformly, pushing the corundum boat to the center of a tube furnace for calcining, and introducing oxygen. The heating rate is 10 ℃/min, the reaction is firstly carried out for 5h under the temperature of 300 ℃, and then the sintering is carried out for 15h under the temperature of 780 ℃, thus obtaining the surface-modified nickel-cobalt lithium aluminate anode material. The specific discharge capacity of the first circle is 186.7mAh g through electrochemical performance test-1. The solution is circulated for 200 circles under the magnification of 2C, and the capacity retention rate is 94.9 percent.
Example 4
Ternary precursor mixed metal hydroxide Ni with lithium metaborate as boron-containing compound0.8Co0.15Al0.05(OH)2After surface pre-coating, the surface modified nickel cobalt lithium aluminate anode material is prepared by high-temperature calcination, and the preparation method comprises the following steps:
(1) preparation of surface pre-coated ternary cathode material precursor
Adding the ternary precursor mixed metal hydroxide and lithium metaborate into a beaker according to the molar ratio of 99:1, adding a certain amount of deionized water, wherein the total content of the mixed metal hydroxide and the lithium metaborate is 50%, stirring and dissolving for 1.5h at 60 ℃, heating to 100 ℃, and continuing stirring until the water is completely evaporated. And transferring the obtained mixture into an oven, and carrying out vacuum drying for 3h at 90 ℃ to obtain the ternary cathode material precursor pre-coated on the surface of the lithium metaborate.
(2) Preparation of surface modified nickel cobalt lithium aluminate anode material
And (3) mixing the obtained surface pre-coated ternary positive electrode material precursor with lithium carbonate according to the molar ratio of 1: 1.05, fully mixing and grinding, transferring the mixed powder into a corundum boat after grinding uniformly, pushing the corundum boat to the center of a tube furnace for calcining, and introducing oxygen. The heating rate is 20 ℃/min, the reaction is firstly carried out for 5h under the temperature of 500 ℃, and then the sintering is carried out for 15h under the temperature of 800 ℃, thus obtaining the surface-modified nickel cobalt lithium aluminate anode material. The specific discharge capacity of the first circle is 188.9mAh g through electrochemical performance test-1. The solution is circulated for 200 circles under the magnification of 2C, and the capacity retention rate is 90.1 percent.
Comparative example 1
Mixing the original ternary precursor mixed metal hydroxide Ni0.8Co0.15Al0.05(OH)2And LiOH in a molar ratio of 1: 1.05, fully mixing and grinding, transferring the mixed powder into a corundum boat after grinding uniformly, pushing the corundum boat to the center of a tube furnace for calcining, and introducing oxygen. The heating rate is 5 ℃/min, the reaction is firstly carried out for 5h under the temperature of 480 ℃, and then the sintering is carried out for 15h under the temperature of 750 ℃, thus obtaining the nickel cobalt lithium aluminate anode material without surface modification. The specific discharge capacity of the first ring is 190.7mAh g through electrochemical performance test-1. The solution is circulated for 200 circles under the magnification of 2C, and the capacity retention rate is 74.5 percent.
In the above examples 1 to 3 and comparative examples, the preparation of the electrode and the electrochemical performance test method thereof were as follows:
n-methylpyrrolidone (NMP) is used as a solvent, polyvinylidene fluoride (PVDF) is used as a binder, and Super P is used as a conductive agent, wherein the PVDF is dissolved in the NMP in advance before use. According to the mass ratio of 80: 10: 10, respectively weighing a nickel-cobalt lithium aluminate anode material, PVDF and a conductive agent Super P, mixing and grinding; coating the slurry obtained by grinding on a bright aluminum foil with the thickness of 9 microns and serving as a current collector, after NMP is completely volatilized, rolling the electrode plate by using a roller press, and punching the electrode plate into an electrode plate with the diameter of 13 mm; then, the electrode slice is placed in a vacuum oven to be dried at 105 ℃ overnight; after the pole pieces are weighed, the pole pieces are quickly transferred into a glove box; taking metal lithium as a counter electrode, Celgard 2400 as a diaphragm, and dissolving 1mol/L LiPF6 as an electrolyte in an EC/DMC/EMC (volume ratio of 1:1:1) mixed solvent. And (3) carrying out electrochemical performance test on the assembled battery, wherein the test equipment is a blue CT2001A constant-current test cabinet, and the test voltage range is 2.8-4.3V.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (6)
1. A surface modified nickel cobalt lithium aluminate anode material is characterized in that: the cathode material consists of a layered material nickel cobalt lithium aluminate cathode active substance and a surface modification layer, wherein the surface modification layer comprises a surface doping modification layer and a boron-containing oxide melt coating layer; the positive electrode material is spherical or spheroidal particles, and the particle size range of the particles is 0.5-20 um; in the boron-containing oxide molten coating layer, the molar ratio of boron element to the positive electrode material is (0.1-5): 100;
the preparation method of the surface-modified nickel cobalt lithium aluminate anode material comprises the following steps:
(1) mixing a boron-containing compound and a ternary precursor with a chemical formula of NixCoyAlz (OH)2 by a wet method to obtain a surface pre-coated ternary cathode material precursor; the wet mixing in the step (1) is specifically as follows: mixing the weighed ternary precursor with a boron-containing compound, adding deionized water to obtain a mixed aqueous solution, dissolving for 0.5-2 hours at the temperature of 30-60 ℃ under stirring, heating to 70-100 ℃, continuing stirring for 3-8 hours until water is completely evaporated, and performing vacuum drying for 3-12 hours at the temperature of 80-120 ℃ to obtain a surface pre-coated ternary cathode material precursor;
(2) and mixing the precursor of the ternary cathode material with the pre-coated surface with lithium salt, calcining at high temperature, and cooling to obtain the surface-modified nickel-cobalt lithium aluminate cathode material.
2. The surface-modified lithium nickel cobalt aluminate positive electrode material of claim 1, wherein: the chemical formula of the cathode material is LiNixCoyAlzO2, wherein x + y + z is 1, x is more than or equal to 0.5 and less than or equal to 0.9, y is more than 0 and less than or equal to 0.3, and z is more than 0 and less than or equal to 0.1.
3. The surface-modified lithium nickel cobalt aluminate positive electrode material of claim 1, wherein: the boron-containing compound in the step (1) is at least one of ammonium borate, boric acid, boron trioxide and lithium metaborate.
4. The surface-modified lithium nickel cobalt aluminate positive electrode material of claim 1, wherein: the total mass of the ternary precursor and the boron-containing compound is 20-50% of the mass of the mixed aqueous solution.
5. The surface-modified lithium nickel cobalt aluminate positive electrode material of claim 1, wherein: the high-temperature calcination in the step (2) comprises a first constant-temperature stage and a second constant-temperature stage, wherein the first constant-temperature stage is 300-500 ℃, the second constant-temperature stage is 720-800 ℃, and the time of the first constant-temperature stage and the time of the second constant-temperature stage are both 0.5-15 h.
6. The surface-modified lithium nickel cobalt aluminate positive electrode material of claim 1, wherein: and (3) in the high-temperature calcination and cooling process in the step (2), controlling the heating rate to be 2-20 ℃/min and the cooling rate to be 0.1 ℃/min, and cooling along with the furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710561502.5A CN107403913B (en) | 2017-07-11 | 2017-07-11 | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710561502.5A CN107403913B (en) | 2017-07-11 | 2017-07-11 | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107403913A CN107403913A (en) | 2017-11-28 |
| CN107403913B true CN107403913B (en) | 2021-02-23 |
Family
ID=60405167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710561502.5A Active CN107403913B (en) | 2017-07-11 | 2017-07-11 | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107403913B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109921013B (en) * | 2017-12-13 | 2022-06-24 | 微宏动力系统（湖州）有限公司 | Modified positive electrode material precursor, preparation method thereof, modified positive electrode material and lithium battery |
| CN108011100A (en) * | 2017-12-15 | 2018-05-08 | 中国科学院成都有机化学有限公司 | A kind of tertiary cathode material of surface reaction cladding and preparation method thereof |
| CN108899516A (en) * | 2018-07-03 | 2018-11-27 | 佛山市德方纳米科技有限公司 | A kind of tertiary cathode material and preparation method thereof |
| CN109360984B (en) * | 2018-12-06 | 2021-02-09 | 济南大学 | Preparation method of layered positive electrode material hybrid surface of lithium ion battery |
| CN109860592B (en) * | 2018-12-25 | 2021-01-29 | 上海力信能源科技有限责任公司 | Boron molecule-modified nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN110085814B (en) * | 2019-01-22 | 2021-07-20 | 蜂巢能源科技有限公司 | Positive electrode material for lithium battery and preparation method and application thereof |
| CN110247045B (en) * | 2019-07-15 | 2020-09-15 | 中南大学 | Nickel-cobalt-manganese ternary cathode material and preparation method and application thereof |
| CN112447950A (en) * | 2019-09-02 | 2021-03-05 | 宁德时代新能源科技股份有限公司 | Positive electrode active material, preparation method thereof, positive electrode plate and lithium ion secondary battery |
| CN111640918A (en) * | 2020-05-11 | 2020-09-08 | 深圳新恒业电池科技有限公司 | Electrode material, preparation method thereof and electrode slice |
| CN112038612B (en) * | 2020-09-16 | 2021-07-30 | 长沙理工大学 | Boron-doped & metaphosphate-coated nickel-based positive electrode material for lithium ion all-solid-state battery and preparation method thereof |
| CN112701271A (en) * | 2020-12-28 | 2021-04-23 | 格林美（无锡）能源材料有限公司 | Element doping method based on ternary precursor positive electrode material |
| CN116639736A (en) * | 2023-05-18 | 2023-08-25 | 新乡天力锂能股份有限公司 | Method for effectively improving water-eluted lithium of high-nickel positive electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332584A (en) * | 2011-10-18 | 2012-01-25 | 无锡晶石新型能源有限公司 | Liquid phase coating method of lithium manganate |
| CN103236537A (en) * | 2013-04-12 | 2013-08-07 | 哈尔滨工业大学 | Lithium ion battery gradient core shell cathode material and synthetic method thereof |
| JP2016201342A (en) * | 2015-04-14 | 2016-12-01 | トヨタ自動車株式会社 | Production method of composite active material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104752712A (en) * | 2013-12-30 | 2015-07-01 | 北京当升材料科技股份有限公司 | A preparing method of a nickel cobalt lithium aluminate cathode material |
| CN104022280B (en) * | 2014-06-27 | 2017-04-12 | 南通瑞翔新材料有限公司 | High-voltage cathode material for lithium ion battery and preparation method thereof |
| CN104218243B (en) * | 2014-07-01 | 2017-04-12 | 宁波金和锂电材料有限公司 | Highly stable lithium nickel cobalt aluminate positive electrode material and its preparation method |
| CN104409700B (en) * | 2014-11-20 | 2018-07-24 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of Ni-based anode material for lithium-ion batteries and preparation method thereof |
| CN105070907B (en) * | 2015-08-31 | 2018-06-05 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery |
| CN105655577B (en) * | 2016-04-14 | 2018-09-11 | 哈尔滨工业大学 | A kind of method that wet method mixes lithium improvement anode material for lithium-ion batteries high temperature solid state reaction |
| CN106784686A (en) * | 2016-12-21 | 2017-05-31 | 烟台卓能电池材料股份有限公司 | A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof |
| CN106654222A (en) * | 2017-01-16 | 2017-05-10 | 广州锂宝新材料有限公司 | High-nickel cathode material, preparation method thereof and lithium ion battery |
| CN106848183A (en) * | 2017-02-24 | 2017-06-13 | 中国科学院新疆理化技术研究所 | A kind of method for improving ternary cathode material of lithium ion battery high rate performance |
-
2017
- 2017-07-11 CN CN201710561502.5A patent/CN107403913B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102332584A (en) * | 2011-10-18 | 2012-01-25 | 无锡晶石新型能源有限公司 | Liquid phase coating method of lithium manganate |
| CN103236537A (en) * | 2013-04-12 | 2013-08-07 | 哈尔滨工业大学 | Lithium ion battery gradient core shell cathode material and synthetic method thereof |
| JP2016201342A (en) * | 2015-04-14 | 2016-12-01 | トヨタ自動車株式会社 | Production method of composite active material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107403913A (en) | 2017-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107403913B (en) | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof | |
| CN114790013B (en) | Sodium ion battery positive electrode active material capable of self-supplementing sodium, preparation method and application thereof | |
| CN108258224B (en) | Ternary positive electrode material with surface coated with metal oxide and preparation method thereof | |
| WO2021083197A1 (en) | Silicon-oxygen composite negative electrode material and method for preparation thereof and lithium-ion battery | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| CN105938899B (en) | A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries | |
| CN111762768B (en) | Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof | |
| CN103904321B (en) | The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4 | |
| CN106410182B (en) | A kind of preparation method of high compacted density micron order monocrystalline tertiary cathode material | |
| CN108172803B (en) | Surface-modified coated lithium-rich material, preparation method thereof and lithium ion battery | |
| CN109119624B (en) | Preparation method of lithium titanium phosphate coated lithium-rich manganese-based positive electrode material | |
| CN109659511B (en) | SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN108987683A (en) | A kind of preparation method of carbon coating tertiary cathode material | |
| CN110797529A (en) | Doped high-nickel high-voltage NCM positive electrode material and preparation method thereof | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN113782715A (en) | Preparation method and application of lithium phosphate modified high-nickel cobalt lithium manganate positive electrode material | |
| CN113582253B (en) | Quaternary positive electrode material, and preparation method and application thereof | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| WO2014071724A1 (en) | Lithium-rich anode material, lithium battery anode, and lithium battery | |
| CN105655579A (en) | Lithium nickel-cobalt aluminate electrode material and preparation method and application thereof | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN109461917B (en) | Preparation method of lanthanum zirconate in-situ coated high-nickel ternary cathode material | |
| GB2621290A (en) | Template growth method for preparing lithium cobaltate precursor and use thereof | |
| CN106159220A (en) | Two-step method prepares anode material for lithium-ion batteries LiNi0.80co0.15al0.05o2method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180330 Address after: 610041 Chengdu hi tech Zone, East Road, high tech building Applicant after: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences Applicant after: University of Chinese Academy of Sciences Address before: 610041 Chengdu hi tech Zone, East Road, high tech building Applicant before: Chengdu Organic Chemicals Co., Ltd., Chinese Academy of Sciences |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |