CN115259242B - Carbon-based precursor material, positive electrode material and preparation method - Google Patents
Carbon-based precursor material, positive electrode material and preparation method Download PDFInfo
- Publication number
- CN115259242B CN115259242B CN202210996562.0A CN202210996562A CN115259242B CN 115259242 B CN115259242 B CN 115259242B CN 202210996562 A CN202210996562 A CN 202210996562A CN 115259242 B CN115259242 B CN 115259242B
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- equal
- precursor
- carbon
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- 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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly discloses a precursor material, a positive electrode material and a preparation method. The precursor material is of a core-shell structure, wherein the core is Ni with a corrugated carbon-based structure coating layer x1 Co y1 M 1‑x1‑y1 (OH) 2 X1 is more than 0 and less than or equal to 1, y1 is more than or equal to 0 and less than or equal to 0.2, and M is at least one of Mn, al, zr, W, nb, ti, Y; ni with shell in layered structure x2 Co y2 N 1‑x2‑y2 (OH) 2 X2 is more than 0 and less than or equal to 1, y2 is more than or equal to 0 and less than or equal to 0.2, and N is at least one of Mn, al, zr, W, nb, ti, Y. In the preparation process, ni is firstly obtained x1 Co y1 M 1‑x1‑y1 (OH) 2 Seed crystal, then carbon modification and group modification are carried out; and taking the modified material as seed crystal again, and preparing the precursor material by coprecipitation. And mixing the precursor materials with lithium, and sintering to obtain the anode material. A carbon layer may be further deposited on the surface of the positive electrode material. The positive electrode material prepared by the method has good conductivity, and the volume expansion is relieved, so that lithium ions are inserted more easily through lithium, and the diffusion rate of lithium is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a positive electrode material and a precursor thereof.
Background
The lithium ion battery has the excellent performances of high working voltage, high energy density, long cycle life, small self-discharge rate, low pollution, no memory effect and the like, and becomes a research and application hot spot of the secondary battery. The lithium ion battery has wide application prospect in the fields of new energy electric automobiles, digital products, mobile phones and the like, but with the continuous development of the electric automobile industry, the lithium ion battery has higher and higher requirements on the safety, the specific charge-discharge capacity and the cycle life of energy products (lithium ion batteries).
The positive electrode material is taken as an important component of the lithium ion battery, wherein the ternary positive electrode material has become the main stream of the current market due to the advantages of high capacity and high energy density. The synthesized positive electrode material with high safety performance, excellent cruising ability and long service life is popular in the market.
The production of the main stream ternary positive electrode material in the current market mainly comprises the steps of synthesizing a precursor, further sintering and attaching lithium, wherein the ternary positive electrode material is in continuous with the internal crystal structure of the precursor, and the great specific gravity of the precursor determines the performance of the positive electrode material.
The ternary positive electrode material precursor is mainly divided into a secondary sphere and a monocrystal product, the corresponding positive electrode material inherits respective advantages and disadvantages, the secondary sphere is easy to crack due to overlarge granularity, and the interface is broken in the charging and discharging process, but has the characteristic of excellent multiplying power performance; the single crystal has relatively few grain boundaries, relatively firm structure, less breakage in the charge and discharge process, excellent cycle performance and relatively low rate performance.
Aiming at the problems of the electrode materials, the current common strategies mainly comprise two types, namely optimization of the internal structure of the precursor materials (rearrangement of reforming crystal face arrangement and element distribution) and composite base materials (carbon base, titanium base, oxide, lithium-attached oxide and the like).
Disclosure of Invention
In view of the problems of the prior art, it is an object of the present invention to provide a precursor material. It is a second object of the present invention to provide a method for preparing a precursor material. The third object of the present invention is to provide a positive electrode material.
In order to achieve the above object, the present invention provides the following specific technical solutions.
First, the invention provides a precursor material which is of a core-shell structure, wherein the core is Ni with a corrugated carbon-based structure coating layer x1 Co y1 M 1-x1-y1 (OH) 2 X1 is more than 0 and less than or equal to 1, y1 is more than or equal to 0 and less than or equal to 0.2, and M is at least one of Mn, al, zr, W, nb, ti, Y; ni with shell in layered structure x2 Co y2 N 1-x2-y2 (OH) 2 X2 is more than 0 and less than or equal to 1, y2 is more than or equal to 0 and less than or equal to 0.2, and N is at least one of Mn, al, zr, W, nb, ti, Y.
Secondly, the invention provides a preparation method of the precursor material, which comprises the following steps:
step S1, synthesizing Ni by a coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 ；
Step S2, ni is added x1 Co y1 M 1-x1-y1 (OH) 2 Placing the mixture in a heating device, introducing protective gas, and heating; after the temperature is raised to the target temperature, introducing carbon source gas and auxiliary gas, reacting for a period of time, and then cooling;
s3, carrying out surface group modification on the material obtained in the step S2;
and S4, taking the material obtained in the step S3 as seed crystals, and preparing a precursor material by a coprecipitation method.
Further, in a part of the preferred embodiment of the present invention, ni is synthesized in a coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 In the process, the reaction atmosphere is controlled to be air atmosphere or oxygen atmosphere.
Air atmosphere or oxygen atmosphere can be used for Ni x1 Co y1 M 1-x1-y1 (OH) 2 The surface is subjected to oxidation modification to provide adsorption sites for growing the corrugated carbon-based structure.
Further, in a part of the preferred embodiment of the present invention, ni is synthesized in a coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 In the process, the reaction atmosphere is controlled to be nitrogen atmosphere, and meanwhile, the organic dispersing agent is added.
The nitrogen atmosphere is favorable for forming a relatively compact structure, and the organic dispersing machine can slow down agglomeration in the growth process of the precursor seed crystal and simultaneously modify the surface to provide adsorption sites for growing the corrugated carbon-based structure.
Further, the organic dispersing agent is at least one of PVP, polyvinylpyrrolidone, starch and polyvinyl butyral.
Further, in some preferred embodiments of the present invention, the heating rate in step S2 is 1 to 20 ℃/min.
Further, in some preferred embodiments of the present invention, the target temperature in step S2 is 800-1100 ℃.
Further, in a part of the preferred embodiments of the present invention, the carbon source gas is at least one of methane, acetylene, and propane; the auxiliary gas is at least one of ammonia, hydrogen and carbon dioxide; the shielding gas is argon or nitrogen.
Further, in the mixed gas composed of the carbon source gas and the auxiliary gas, the concentration of the carbon source gas is 5-50%.
Further, in a part of the preferred embodiments of the present invention, the group modification in step S3 is one of hydroxylation modification, oxidation modification, acidification modification and alkalization modification.
Further preferably, the hydroxylation modification is performed using a resin (epoxy resin or phenolic resin) or PVP (polyvinylpyrrolidone); performing oxidation modification by using oxygen or hydrogen peroxide; acidifying modification is carried out by oxalic acid, acetic acid or carbonic acid; and (3) alkalizing modification by adopting sodium hydroxide or potassium hydroxide.
The invention further provides a positive electrode material which is obtained by mixing and sintering the precursor material with lithium.
Further, in some preferred embodiments of the present invention, the sintering temperature is 700 to 950 ℃.
The invention also provides another positive electrode material, which consists of the positive electrode material and a carbon layer coated on the surface of the positive electrode material.
Further, in a part of the preferred embodiments of the present invention, the surface of the positive electrode material is coated with a carbon layer by: and placing the anode material in a CVD furnace, introducing protective gas, then introducing carbon source gas and auxiliary gas, heating and preserving heat for a period of time.
The invention further discovers that when a carbon layer is deposited in a CVD furnace, the cracking and dehydrogenation of the carbon source gas can be controlled by changing the ratio of the carbon source gas to the auxiliary gas, and carbon-based materials with different sheet-shaped arrangements can be formed. The radial arrangement of the carbon base can be effectively changed by adjusting the proportion concentration of the auxiliary gas. As the concentration of the assist gas increases, the proportion of radially arranged carbon-based groups increases.
Further, the CVD furnace is a static furnace.
Further, the temperature of the heat preservation is 900-1200 ℃.
Further, the heating rate during heating is 1-20 ℃/min.
According to the invention, the carbon-based material is grown by modifying the surface of the seed crystal, and the precursor with clear wavy carbon-based material is formed by directionally guiding the arrangement of the precursor of the layered structure based on the modified composite material as a template. The cathode material is combined with the carbon-based material to guide the crystal face arrangement of the precursor, recombine lithium ion channels, improve conductivity and reduce internal stress. A layer of firm carbon shell is coated on the surface of the positive electrode material to synthesize the positive electrode material with the wavy grain and double halation structure, so that the volume change of the positive electrode material in the charge and discharge process is greatly improved, and the cycle performance is improved.
Compared with the prior art, the invention has the following obvious beneficial technical effects:
according to the invention, the precursor with special morphology is formed by modifying the surface of the seed crystal of the precursor and then directionally guiding the reformation of the crystal face. The positive electrode material obtained on the basis has good conductivity, and the volume expansion is relieved, so that lithium ions are inserted through lithium more easily, and the diffusion rate of lithium is improved.
The preparation method provided by the invention is simple and stable, is easy for industrial production and is beneficial to large-scale application.
Drawings
Fig. 1 is a schematic diagram of a process for preparing a precursor and a positive electrode material.
FIG. 2 is an SEM image of the interface-modified seed crystal of example 1.
Fig. 3 is an XRD pattern of the precursor prepared in example 1 and comparative example 1.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
As shown in fig. 1, the surface of the seed crystal was modified, and the seed crystal was grown in a stacked manner along the normal direction of the (001) crystal plane, to form a corrugated carbon-based seed crystal. Then, on the basis of the seed crystal, the precursor is grown secondarily. And after sintering the precursor and lithium at high temperature, further depositing carbon by a CVD process to obtain the anode material with the halation carbon shell layer.
The seed crystal prepared by the coprecipitation method can be binary material, ternary material or multi-element material, and can also contain doping elements.
The shell of the secondary growth precursor can also be binary material, ternary material or multi-element material, and can also contain doping elements.
Example 1
The embodiment comprises the following steps:
(1) Seed crystal Ni with particle diameter of about 1 μm is synthesized by a coprecipitation method by using a 50L reaction kettle 0.85 Co 0.05 Mn 0.1 (OH) 2 The oxygen content in the kettle is controlled to be 10-15%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protection gas, and heating at a heating rate of 5 ℃/min.
(3) When the temperature was raised to 1000 ℃, a mixed gas of propane and hydrogen (the concentration of propane in the mixed gas was 5%) was introduced, and after 1 hour of reaction, the temperature was lowered.
(4) And (3) placing the sample collected in the step (3) into a polyvinylpyrrolidone solution for soaking for 1h, and drying to collect the sample.
(5) And (3) putting the sample collected in the step (4) into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be 11-12 and the ammonia concentration to be 4-8g/L, and obtaining a precursor. The shell layer of the precursor is Ni 0.65 Co 0.1 Mn 0.35 (OH) 2 。
(6) Mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1:1.05, calcining at 900 ℃ for 10 hours, then placing into a CVD furnace, introducing protective gas to exhaust air, heating to 1000 ℃ at a heating speed of 10 ℃/min, and preserving heat for 3 hours to carry out carbon coating.
Fig. 2 is an SEM image of the sample obtained in step (4), and it can be seen that the material is spherical and has a wavy structure on the surface.
Comparative example 1
The method comprises the following steps:
(1) Seed crystal Ni with particle diameter of about 1 μm is synthesized by a coprecipitation method by using a 50L reaction kettle 0.85 Co 0.05 Mn 0.1 (OH) 2 The oxygen content in the kettle is controlled to be 10-15%.
(2) Ni is obtained in the step (1) as seed crystal 0.85 Co 0.05 M 0.1 (OH) 2 Putting the mixture into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be 11-12 and the ammonia concentration to be 4-8g/L, and obtaining the precursor. The precursor shell layer is Ni 0.65 Co 0.1 Mn 0.35 (OH) 2 。
(3) And (3) mixing the precursor in the step (2) with lithium hydroxide according to a molar ratio of 1:1.05, and calcining at 900 ℃ for 10 hours to obtain the positive electrode material.
Fig. 2 is an XRD pattern of the precursor prepared in example 1 and comparative example 1. It is understood from the calculation of the characteristic crystal face ratio I (001)/I (101) that the characteristic crystal face ratio of the precursor prepared in example 1 was 0.97, and the characteristic crystal face ratio of the precursor prepared in comparative example 1 was 1.83.
Example 2
The embodiment comprises the following steps:
(1) Seed crystal Ni with particle diameter of about 2 mu m is synthesized by a coprecipitation method by using a 100L reaction kettle 0.7 Co 0.1 Mn 0.2 (OH) 2 The oxygen content in the kettle is controlled to be 8-12%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protection gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature is raised to 1100 ℃, mixed gas of methane and ammonia (the concentration of methane in the mixed gas is 20%) is introduced, and after 0.5h of reaction, the temperature is reduced.
(4) And (3) placing the sample collected in the step (3) into epoxy resin, soaking for 1h, and drying to collect the sample.
(5) Putting the sample collected in the step (4) into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be between 10 and 11 and the ammonia concentration to be between 6 and 10g/L to obtain a precursor, wherein a shell layer of the precursor is Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 。
(6) Mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1:1.1, calcining at 800 ℃ for 12 hours, then placing the mixture into a CVD furnace, introducing protective gas to exhaust air, heating to 1200 ℃ at a heating speed of 6 ℃/min, and preserving heat for 5 hours to carry out carbon coating.
Example 3
The embodiment comprises the following steps:
(1) Using 10m 3 Seed crystal Ni with the grain diameter of about 3 mu m is synthesized in a reaction kettle by a coprecipitation method 0.68 Co 0.1 Mn 0.12 (OH) 2 The oxygen content in the kettle is controlled to be 4-8%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protection gas, and heating at a heating rate of 15 ℃/min.
(3) When the temperature is raised to 800 ℃, mixed gas of methane and hydrogen (the concentration of methane in the mixed gas is 30%) is introduced, and after 1h of reaction, the temperature is reduced.
(4) And (3) placing the sample collected in the step (3) into a polyvinylpyrrolidone solution for soaking for 1h, and drying to collect the sample.
(5) And (3) putting the sample collected in the step (4) into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be 10-11 and the ammonia concentration to be 8-12g/L, and obtaining a precursor. The precursor shell layer is Ni 0.68 Co 0.1 Mn 0.12 (OH) 2 。
(6) Mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1:1.07, calcining at 700 ℃ for 8 hours, placing in a CVD furnace, introducing protective gas to exhaust air, heating to 1200 ℃ at a heating speed of 15 ℃/min, and preserving heat for 5 hours to perform carbon coating.
Example 4
The embodiment comprises the following steps:
(1) Using 10m 3 Seed crystal Ni with particle diameter of about 4 mu m is synthesized in a reaction kettle by a coprecipitation method 0.5 Co 0.2 Mn 0.3 (OH) 2 The oxygen content in the kettle is controlled to be 3-5%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protection gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature was raised to 900 ℃, a mixed gas of propane and hydrogen (the concentration of propane in the mixed gas was 20%) was introduced, and after 0.5 hour of reaction, the temperature was lowered.
(4) And (3) placing the sample collected in the step (3) into hydrogen peroxide solution for soaking for 1h, and drying to collect the sample.
(5) And (3) putting the sample collected in the step (4) into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be between 10 and 12 and the ammonia concentration to be between 4 and 10g/L, and obtaining a precursor. The shell layer of the precursor is Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 。
(6) Mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1:1.05, calcining for 12 hours at 950 ℃, putting into a CVD furnace, introducing protective gas to exhaust air, heating to 1200 ℃ at a heating speed of 15 ℃/min, and preserving heat for 5 hours to perform carbon coating.
Example 5
(1) Using 10m 3 Seed crystal Ni with particle diameter of about 4 mu m is synthesized in a reaction kettle by a coprecipitation method 0.9 Co 0.05 M n0.05 (OH) 2 The synthesis process is nitrogen atmosphere, a proper amount of phenolic resin with the concentration of 30% is added, and the oxygen content in the kettle is controlled to be 1-2%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protection gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature is raised to 1050 ℃, methane and hydrogen are introduced, the methane concentration is controlled to be 25%, and after 0.5h of reaction, the temperature is reduced.
(4) And (3) drying the sample collected in the step (3) and collecting the sample.
(5) And (3) putting the sample collected in the step (4) into a reaction kettle for coprecipitation reaction, controlling the pH of the reaction to be between 10 and 12 and the ammonia concentration to be between 4 and 10g/L, and obtaining a precursor. The shell layer of the precursor is Ni 0.9 Co 0.05 M n0.05 (OH) 2 。
(6) Mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1:1.07, calcining for 12 hours at 950 ℃, putting into a CVD furnace, introducing protective gas to exhaust air, heating to 1200 ℃ at a heating speed of 15 ℃/min, and preserving heat for 5 hours to perform carbon coating.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (15)
1. The precursor material is characterized by being of a core-shell structure, wherein the core is Ni with a carbon-based structure coating layer with wavy grains x1 Co y1 M 1-x1-y1 (OH) 2 X1 is more than 0 and less than or equal to 1, y1 is more than or equal to 0 and less than or equal to 0.2, and M is at least one of Mn, al, zr, W, nb, ti, Y; ni with shell in layered structure x2 Co y2 N 1-x2-y2 (OH) 2 X2 is more than 0 and less than or equal to 1, y2 is more than or equal to 0 and less than or equal to 0.2, and N is at least one of Mn, al, zr, W, nb, ti, Y.
2. The method of preparing a precursor material according to claim 1, comprising the steps of:
step S1, synthesizing Ni by a coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 ；
Step S2, ni is added x1 Co y1 M 1-x1-y1 (OH) 2 Placing the mixture in a heating device, introducing protective gas, and heating; after the temperature is raised to the target temperature, introducing carbon source gas and auxiliary gas, reacting for a period of time, and then cooling;
s3, carrying out surface group modification on the material obtained in the step S2;
and S4, taking the material obtained in the step S3 as seed crystals, and preparing a precursor material by a coprecipitation method.
3. The preparation method according to claim 2, wherein Ni is synthesized by coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 In the process, the reaction atmosphere is controlled to be air atmosphere or oxygen atmosphere.
4. The preparation of claim 2The method is characterized in that Ni is synthesized by a coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 In the process, the reaction atmosphere is controlled to be nitrogen atmosphere, and meanwhile, the organic dispersing agent is added.
5. The method according to claim 4, wherein the organic dispersant is at least one of PVP, polyvinylpyrrolidone, starch, and polyvinyl butyral.
6. The preparation method according to any one of claims 2 to 5, wherein the heating rate in step S2 is 1 to 20 ℃/min; and the target temperature in the step S2 is 800-1100 ℃.
7. The production method according to any one of claims 2 to 5, wherein the carbon source gas is at least one of methane, acetylene and propane; the auxiliary gas is at least one of ammonia, hydrogen and carbon dioxide; the shielding gas is argon or nitrogen.
8. The method according to claim 7, wherein the concentration of the carbon source gas in the mixed gas of the carbon source gas and the assist gas is 5 to 50%.
9. The method of claim 2, wherein the modification of the group in step S3 is one of hydroxylation, oxidation, acidification and basification.
10. The method of claim 9, wherein the hydroxylation modification is performed using a resin or PVP; performing oxidation modification by using oxygen or hydrogen peroxide; acidifying modification is carried out by oxalic acid, acetic acid or carbonic acid; and (3) alkalizing modification by adopting sodium hydroxide or potassium hydroxide.
11. A positive electrode material, characterized in that it is obtained by lithium-mixed sintering of the precursor material according to claim 1.
12. The positive electrode material of claim 11, wherein the sintering temperature is 700-950 ℃.
13. A positive electrode material, comprising the positive electrode material according to claim 11 or 12 and a carbon layer coated on the surface of the positive electrode material according to claim 11 or 12.
14. The positive electrode material of claim 13, wherein the surface of the positive electrode material is coated with the carbon layer by: and placing the anode material in a CVD furnace, introducing protective gas, then introducing carbon source gas and auxiliary gas, heating and preserving heat for a period of time.
15. The positive electrode material of claim 14, wherein the CVD furnace is a static furnace; the temperature of the heat preservation is 900-1200 ℃; the heating rate during heating is 1-20 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210996562.0A CN115259242B (en) | 2022-08-19 | 2022-08-19 | Carbon-based precursor material, positive electrode material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210996562.0A CN115259242B (en) | 2022-08-19 | 2022-08-19 | Carbon-based precursor material, positive electrode material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115259242A CN115259242A (en) | 2022-11-01 |
| CN115259242B true CN115259242B (en) | 2023-05-16 |
Family
ID=83752532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210996562.0A Active CN115259242B (en) | 2022-08-19 | 2022-08-19 | Carbon-based precursor material, positive electrode material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115259242B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715424A (en) * | 2014-01-06 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Core-shell structured cathode material and preparation method thereof |
| CN107585794A (en) * | 2017-09-13 | 2018-01-16 | 中南大学 | Tertiary cathode material, its presoma and the preparation method of the material and presoma |
| CN108172799A (en) * | 2017-12-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof |
| CN109768231A (en) * | 2018-11-19 | 2019-05-17 | 上海紫剑化工科技有限公司 | A kind of nickelic tertiary cathode material of monocrystalline type and preparation method thereof |
| CN109817925A (en) * | 2019-01-24 | 2019-05-28 | 广东凯金新能源科技股份有限公司 | Lithium ion secondary battery Si oxide composite negative pole material and preparation method |
| WO2020029029A1 (en) * | 2018-08-06 | 2020-02-13 | 中天新兴材料有限公司 | Preparation method for positive electrode material, positive electrode material and lithium ion battery |
| CN110817978A (en) * | 2019-11-13 | 2020-02-21 | 河北彩客化学股份有限公司 | Positive electrode material precursor for lithium battery and preparation method thereof |
| CN113889624A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Carbon-coated ternary cathode material and preparation method and application thereof |
| WO2022083120A1 (en) * | 2020-10-20 | 2022-04-28 | 湖南长远锂科股份有限公司 | Positive electrode material of lithium ion battery, and preparation method therefor |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3066708B1 (en) * | 2013-11-08 | 2018-07-25 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften | Method of manufacturing an electrode material, electrode material and vehicle comprising a battery including such an electrode material |
| CN104409716A (en) * | 2014-10-30 | 2015-03-11 | 中国科学院过程工程研究所 | Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof |
| CN110867576A (en) * | 2018-08-28 | 2020-03-06 | 比亚迪股份有限公司 | Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile |
-
2022
- 2022-08-19 CN CN202210996562.0A patent/CN115259242B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103715424A (en) * | 2014-01-06 | 2014-04-09 | 中国科学院宁波材料技术与工程研究所 | Core-shell structured cathode material and preparation method thereof |
| CN107585794A (en) * | 2017-09-13 | 2018-01-16 | 中南大学 | Tertiary cathode material, its presoma and the preparation method of the material and presoma |
| CN108172799A (en) * | 2017-12-28 | 2018-06-15 | 清远佳致新材料研究院有限公司 | A kind of tertiary cathode material of nucleocapsid structure lithium ion battery and preparation method thereof |
| WO2020029029A1 (en) * | 2018-08-06 | 2020-02-13 | 中天新兴材料有限公司 | Preparation method for positive electrode material, positive electrode material and lithium ion battery |
| CN109768231A (en) * | 2018-11-19 | 2019-05-17 | 上海紫剑化工科技有限公司 | A kind of nickelic tertiary cathode material of monocrystalline type and preparation method thereof |
| CN109817925A (en) * | 2019-01-24 | 2019-05-28 | 广东凯金新能源科技股份有限公司 | Lithium ion secondary battery Si oxide composite negative pole material and preparation method |
| CN110817978A (en) * | 2019-11-13 | 2020-02-21 | 河北彩客化学股份有限公司 | Positive electrode material precursor for lithium battery and preparation method thereof |
| CN113889624A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Carbon-coated ternary cathode material and preparation method and application thereof |
| WO2022083120A1 (en) * | 2020-10-20 | 2022-04-28 | 湖南长远锂科股份有限公司 | Positive electrode material of lithium ion battery, and preparation method therefor |
Non-Patent Citations (3)
| Title |
|---|
| MWCNTs-GONRs/Co3O4@Ni(OH)2core-shell array structure with a high performance electrode for supercapacitor;Hengrui Qiu;Chemical Engineering Journal;第380卷;全文 * |
| Synthesis and electrochemical investigation of core-shell ultrathin NiO nanosheets grown on hollow carbon microspheres composite for high performance lithium and sodium ion batteries;Beibei Wang;Chemical Engineering Journal;第306卷;1193–1202 * |
| 碳包覆Ni/Y_2O_3纳米颗粒的制备与表征;郑朝晖;李凤岐;安玉良;袁霞;张罡;;辽宁化工(第12期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115259242A (en) | 2022-11-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111082006B (en) | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN110233250B (en) | Preparation method of single crystal particle ternary cathode material | |
| US5914094A (en) | Process for preparing cathode active material by a sol-gel method | |
| JP2022550265A (en) | Cobalt-free positive electrode material, manufacturing method thereof, and lithium ion battery | |
| CN110993903B (en) | Tantalum modified high-nickel cathode material and preparation method and application thereof | |
| CN110518213A (en) | A kind of porous silicon-carbon nano tube compound material and its preparation method and application | |
| CN108054371A (en) | A kind of high-tap density, high magnification and long-life lithium-rich manganese-based anode material and preparation method thereof | |
| CN115043440A (en) | Lithium ion battery positive electrode material precursor, preparation method and application thereof, lithium ion battery positive electrode material, preparation method and application thereof | |
| CN110707311B (en) | High-nickel ternary material and nano zinc oxide composite cathode material and preparation method thereof | |
| CN112349885A (en) | Modified lithium ion battery positive electrode material and preparation method thereof | |
| CN112499631A (en) | Fe3C/C composite material and application thereof | |
| CN114702022B (en) | Preparation method and application of hard carbon anode material | |
| CN109286001A (en) | A kind of modified lithium nickelate preparation method | |
| CN115954443A (en) | Preparation method of carbon-coated silicon-copper alloy negative electrode material of lithium ion battery | |
| CN111170369A (en) | Lithium manganate or lithium nickel manganese material and preparation method and application thereof | |
| CN114314564A (en) | Carbon nanotube conductive network coated SiO @ C composite material and preparation method and application thereof | |
| CN111029541B (en) | Silicon-carbon composite electrode material for honeycomb-like lithium ion battery and preparation method thereof | |
| CN115312736B (en) | Preparation method of Si@TiN-asphalt composite anode material | |
| CN115259242B (en) | Carbon-based precursor material, positive electrode material and preparation method | |
| CN115140783B (en) | Ternary positive electrode material precursor, and preparation method and application thereof | |
| CN105375004B (en) | Long-life high-energy lithium secondary battery positive electrode material and preparation method thereof | |
| CN110993917B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN113363450A (en) | Preparation method of carbon nano tube coated high-nickel ternary cathode composite material | |
| CN108493406B (en) | Application of high-nickel ternary cathode material as catalyst in preparation of carbon nanotube, cathode material and preparation method thereof, and lithium battery | |
| CN111653765A (en) | Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |