CN115259242A - 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
- CN115259242A CN115259242A CN202210996562.0A CN202210996562A CN115259242A CN 115259242 A CN115259242 A CN 115259242A CN 202210996562 A CN202210996562 A CN 202210996562A CN 115259242 A CN115259242 A CN 115259242A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- equal
- modification
- gas
- 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.)
- Granted
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 wavy 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, M is at least one of Mn, al, zr, W, nb, ti and Y; ni with shell of laminated 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, N is at least one of Mn, al, zr, W, nb, ti and Y. In the preparation process, first Ni is obtained x1 Co y1 M 1‑x1‑y1 (OH) 2 Seed crystal, then carrying out carbon modification and group modification; and taking the modified material as a seed crystal again, and performing coprecipitation to prepare the precursor material. And mixing and sintering the precursor material with lithium to obtain the cathode material. And further depositing a carbon layer on the surface of the cathode material. The cathode material prepared by the invention has better conductivity, relieves the volume expansion, ensures that lithium ions are easier to be intercalated and inserted, and improves the diffusion rate of lithium.
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 advantages of high working voltage, large energy density, long cycle life, small self-discharge rate, low pollution, no memory effect and the like, and becomes a secondary battery research and application hotspot. The lithium ion battery has a wide application prospect in the fields of new energy electric vehicles, digital products, mobile phones and the like, but with the continuous development of the electric vehicle industry, the lithium ion battery has higher and higher requirements on the safety, the charge-discharge specific capacity and the cycle life of the energy products (lithium ion batteries).
The positive electrode material is used as an important component of the lithium ion battery, wherein the ternary positive electrode material has become the mainstream 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 mainstream ternary cathode material in the current market is mainly produced by firstly synthesizing a precursor and then further sintering to attach lithium, the ternary cathode material inherits the internal crystal structure of the precursor, and the quality of the precursor and the specific gravity determine the performance of the cathode material.
The ternary anode material precursor is mainly divided into a secondary ball and a single crystal product, the corresponding anode material inherits respective advantages and disadvantages, the secondary ball is easy to crack due to overlarge granularity, and an interface is broken in the charging and discharging process, but the ternary anode material precursor has the characteristic of excellent rate performance; because the crystal boundary of the single crystal is relatively less, the structure is relatively firm, the single crystal is less broken in the charging and discharging process, the cycle performance is excellent, and the multiplying power performance is relatively low.
For the problems of the electrode materials, two strategies are mainly used at present, one is optimization of the internal structure of the precursor material (reforming crystal face arrangement and element distribution rearrangement), and the other is a composite base material (carbon-based, titanium-based, 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. Another object of the present invention is to provide a method for preparing a precursor material. The invention also aims to provide a positive electrode material.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a precursor material which is of a core-shell structure, wherein the core is Ni with a wavy 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, M is at least one of Mn, al, zr, W, nb, ti and Y; ni with shell of laminated 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, N is at least one of Mn, al, zr, W, nb, ti and Y.
Secondly, the invention provides a preparation method of the precursor material, which comprises the following steps:
s1, synthesizing Ni by coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 ；
Step S2, adding Ni x1 Co y1 M 1-x1-y1 (OH) 2 Placing the mixture in a heating device, introducing protective gas, and then heating; when the temperature is raised to the target temperature, introducing carbon source gas and auxiliary gas, reacting for a period of time, and cooling;
s3, performing surface group modification on the material obtained in the step S2;
and S4, taking the material obtained in the step S3 as a seed crystal, and preparing a precursor material by a coprecipitation method.
Further, in some preferred embodiments 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.
The air atmosphere or the oxygen atmosphere may be applied to Ni x1 Co y1 M 1-x1-y1 (OH) 2 The surface is oxidized and modified to provide adsorption sites for the growth of the corrugated carbon-based structure.
Further, in some preferred embodiments 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, the organic dispersing machine can slow down agglomeration in the growth process of the precursor crystal seeds, and meanwhile, the surface is modified to provide adsorption sites for the long-wave corrugated carbon-based structure.
Further, the organic dispersant is at least one of PVP, polyvinylpyrrolidone, starch and polyvinyl butyral.
Further, in some preferred embodiments of the present invention, the temperature increase 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 to 1100 ℃.
Further, in some 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 gas, hydrogen gas and carbon dioxide; the protective gas is argon or nitrogen.
Further, the concentration of the carbon source gas in the mixed gas of the carbon source gas and the auxiliary gas is 5 to 50%.
Further, in some preferred embodiments of the present invention, the group modification manner 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 phenol resin) or PVP (polyvinylpyrrolidone); carrying out oxidation modification by using oxygen or hydrogen peroxide; carrying out acidification modification by using oxalic acid, acetic acid or carbonic acid; and (3) carrying out alkalization modification by adopting sodium hydroxide or potassium hydroxide.
The invention also 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 some preferred embodiments of the present invention, the surface of the positive electrode material is coated with a carbon layer by: and (3) placing the anode material in a CVD furnace, introducing protective gas, then introducing carbon source gas and auxiliary gas, and heating and preserving heat for a period of time.
The invention further discovers that carbon-based materials in different sheet arrangements can be formed by changing the ratio of the carbon source gas to the auxiliary gas to control the cracking dehydrogenation of the carbon source gas when the carbon layer is deposited in the CVD furnace. The radial arrangement of carbon base can be effectively changed by adjusting the proportional concentration of the auxiliary gas. As the concentration of the assist gas increases, the proportion of radially arranged carbon radicals increases.
Further, the CVD furnace is a static furnace.
Further, the temperature of the heat preservation is 900 to 1200 ℃.
Further, the heating rate during heating is 1 to 20 ℃/min.
According to the invention, the surface of the seed crystal is modified to grow the carbon-based material, and the precursor of the layered structure is directionally guided to be arranged based on the modified composite material serving as a template, so that the precursor of the carbon-based material with clear wavy veins is formed. The anode material is combined with the carbon-based material to guide the crystal face arrangement of the precursor, recombine the lithium ion channel, improve the conductivity and reduce the internal stress. A layer of firm carbon shell is coated on the surface of the anode material, the anode material with the wavy texture and the double-halo structure is synthesized, the volume change of the anode material in the charge-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:
the method forms the precursor with special morphology by directionally guiding crystal face reforming after modifying the crystal seed surface of the precursor. The cathode material obtained on the basis has better conductivity, relieves the volume expansion, ensures that lithium ions are inserted by being easier to insert lithium, and improves the diffusion rate of lithium.
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 cathode material.
Fig. 2 is an SEM image of the seed crystal after the interface modification of example 1.
Fig. 3 is an XRD pattern of the precursors prepared in example 1 and comparative example 1.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art 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 limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
As shown in fig. 1, the surface of the seed crystal is modified, and the seed crystal grows in a stacking manner along the normal direction of the (001) plane, thereby forming a corrugated carbon-based seed crystal. And secondly growing the precursor on the basis of the seed crystal. And after sintering the precursor and lithium at high temperature, further depositing carbon by a CVD (chemical vapor deposition) process to obtain the anode material with the halo carbon shell layer.
The crystal seed prepared by the coprecipitation method can be a binary material, a ternary material or a multi-component material, and can also contain doping elements.
The shell of the secondary growth precursor can also be a binary material, a ternary material or a multi-element material, and can also contain a doping element.
Example 1
The embodiment comprises the following steps:
(1) Synthesis of seed Ni having a particle size of about 1 μm by coprecipitation method in a 50L reactor 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 protective gas, and heating at a heating rate of 5 ℃/min.
(3) When the temperature rises to 1000 ℃, the mixed gas of propane and hydrogen (the concentration of propane in the mixed gas is 5%) is introduced, and the temperature is reduced after 1h of reaction.
(4) And (4) soaking the sample collected in the step (3) in a polyvinylpyrrolidone solution for 1h, and then drying and collecting the sample.
(5) And (4) putting the sample collected in the step (4) into a reaction kettle, carrying out coprecipitation reaction, and controlling the reaction pH to be between 11 and 12 and the ammonia concentration to be between 4 and 8g/L to obtain the precursor. The shell layer of the precursor is Ni 0.65 Co 0.1 Mn 0.35 (OH) 2 。
(6) And (3) mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1.05, calcining at 900 ℃ for 10h, then putting into a CVD (chemical vapor deposition) furnace, introducing protective gas to evacuate air, heating to 1000 ℃ at a heating speed of 10 ℃/min, preserving heat for 3h, and carrying 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 the surface has a wavy texture.
Comparative example 1
The method comprises the following steps:
(1) Synthesis of seed N having a particle size of about 1 μm by coprecipitation method in a 50L reactori 0.85 Co 0.05 Mn 0.1 (OH) 2 And controlling the oxygen content in the kettle to be 10-15%.
(2) Seed crystal Ni obtained in the step (1) 0.85 Co 0.05 M 0.1 (OH) 2 Putting the precursor into a reaction kettle for coprecipitation reaction, and controlling the pH value of the reaction to be 11-12 and the ammonia concentration to be 4-8g/L to obtain the precursor. The precursor shell 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 1.05, and calcining at 900 ℃ for 10h to obtain the cathode material.
Fig. 2 is an XRD pattern of the precursors prepared in example 1 and comparative example 1. By calculating the characteristic crystal plane ratio I (001)/I (101), the characteristic crystal plane ratio of the precursor prepared in example 1 was 0.97, and the characteristic crystal plane ratio of the precursor prepared in comparative example 1 was 1.83.
Example 2
The embodiment comprises the following steps:
(1) Synthesis of seed Ni having a particle size of about 2 μm by coprecipitation method in 100L reactor 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 protective gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature rises to 1100 ℃, mixed gas of methane and ammonia gas (the concentration of methane in the mixed gas is 20%) is introduced, and after 0.5h of reaction, the temperature is reduced.
(4) And (4) soaking the sample collected in the step (3) in epoxy resin for 1h, and drying to collect the sample.
(5) Putting the sample collected in the step (4) into a reaction kettle, carrying out coprecipitation reaction, controlling the reaction pH to be between 10 and 11 and the ammonia concentration to be between 6 and 10g/L, and obtaining a precursor, wherein the precursor shell is Ni 0.7 Co 0.1 Mn 0.2 (OH) 2 。
(6) And (3) mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1.1, calcining at 800 ℃ for 12h, then putting into a CVD (chemical vapor deposition) furnace, introducing protective gas to evacuate air, heating to 1200 ℃ at a heating speed of 6 ℃/min, preserving heat for 5h, and carrying out carbon coating.
Example 3
The embodiment comprises the following steps:
(1) Using 10m 3 Seed crystal Ni with grain diameter of about 3 mu m is synthesized by a reaction kettle through a coprecipitation method 0.68 Co 0.1 Mn 0.12 (OH) 2 And controlling the oxygen content in the kettle to be 4-8%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protective gas, and heating at a heating rate of 15 ℃/min.
(3) When the temperature rises to 800 ℃, the mixed gas of methane and hydrogen (the concentration of methane in the mixed gas is 30%) is introduced, and the temperature is reduced after 1h of reaction.
(4) And (4) soaking the sample collected in the step (3) in a polyvinylpyrrolidone solution for 1h, and then drying and collecting the sample.
(5) And (4) putting the sample collected in the step (4) into a reaction kettle, carrying out coprecipitation reaction, and controlling the reaction pH to be 10-11 and the ammonia concentration to be 8-12g/L to obtain the precursor. The precursor shell is Ni 0.68 Co 0.1 Mn 0.12 (OH) 2 。
(6) And (3) mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1.07, calcining at 700 ℃ for 8h, placing in a CVD furnace, introducing protective gas to evacuate air, heating to 1200 ℃ at a heating speed of 15 ℃/min, preserving heat for 5h, and carrying out carbon coating.
Example 4
The embodiment comprises the following steps:
(1) Using 10m 3 The reaction kettle synthesizes seed crystal Ni with the grain diameter of about 4 mu m by a coprecipitation method 0.5 Co 0.2 Mn 0.3 (OH) 2 Controlling the oxygen content in the kettle to be 3-5%.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protective gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature rises to 900 ℃, mixed gas of propane and hydrogen (the concentration of propane in the mixed gas is 20%) is introduced, and the temperature is reduced after 0.5h of reaction.
(4) And (4) soaking the sample collected in the step (3) in hydrogen peroxide solution for 1h, and then drying and collecting the sample.
(5) And (4) putting the sample collected in the step (4) into a reaction kettle, carrying out coprecipitation reaction, and controlling the reaction pH to be 10-12 and the ammonia concentration to be 4-10g/L to obtain the precursor. The shell layer of the precursor is Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 。
(6) And (3) mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1.05, calcining at 950 ℃ for 12h, putting into a CVD (chemical vapor deposition) furnace, introducing protective gas to evacuate air, heating to 1200 ℃ at a heating speed of 15 ℃/min, preserving heat for 5h, and carrying out carbon coating.
Example 5
(1) Using 10m 3 The reaction kettle synthesizes seed crystal Ni with the grain diameter of about 4 mu m by a coprecipitation method 0.9 Co 0.05 M n0.05 (OH) 2 The synthesis process is nitrogen atmosphere, adding a proper amount of phenolic resin with the concentration of 30 percent, and controlling the oxygen content in the kettle to be 1-2 percent.
(2) And (3) washing and drying the synthesized seed crystal, placing the seed crystal in a pipeline furnace, introducing nitrogen protective gas, and heating at a heating rate of 10 ℃/min.
(3) When the temperature rises to 1050 ℃, methane and hydrogen are introduced, the concentration of methane is controlled to be 25%, and after 0.5 hour of reaction, the temperature is reduced.
(4) Drying the sample collected in the step (3) and collecting.
(5) And (5) putting the sample collected in the step (4) into a reaction kettle, carrying out coprecipitation reaction, and controlling the reaction pH to be 10-12 and the ammonia concentration to be 4-10g/L to obtain the precursor. The shell layer of the precursor is Ni 0.9 Co 0.05 M n0.05 (OH) 2 。
(6) And (3) mixing the precursor in the step (5) with lithium hydroxide according to a molar ratio of 1.07, calcining at 950 ℃ for 12h, putting into a CVD (chemical vapor deposition) furnace, introducing protective gas to evacuate air, heating to 1200 ℃ at a heating speed of 15 ℃/min, preserving heat for 5h, and carrying out carbon coating.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection 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 of 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, M is at least one of Mn, al, zr, W, nb, ti and Y; ni with shell of 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, N is at least one of Mn, al, zr, W, nb, ti and Y.
2. The method of preparing a precursor material of claim 1, comprising the steps of:
s1, synthesizing Ni by coprecipitation method x1 Co y1 M 1-x1-y1 (OH) 2 ；
Step S2, adding Ni x1 Co y1 M 1-x1-y1 (OH) 2 Placing the mixture in a heating device, introducing protective gas, and then heating; when the temperature is raised to the target temperature, introducing carbon source gas and auxiliary gas, reacting for a period of time, and cooling;
s3, performing surface group modification on the material obtained in the step S2;
and S4, taking the material obtained in the step S3 as a seed crystal, and preparing a precursor material by a coprecipitation method.
3. The method of claim 2, wherein Ni is synthesized in a coprecipitation process 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 method of claim 2, wherein Ni is synthesized in a coprecipitation process 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 of claim 4, wherein the organic dispersant is at least one of PVP, polyvinylpyrrolidone, starch, and polyvinyl butyral.
6. The method according to any one of claims 2 to 5, wherein the temperature rise rate in step S2 is 1 to 20 ℃/min; the target temperature in the step S2 is 800 to 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 gas, hydrogen gas and carbon dioxide; the protective gas is argon or nitrogen.
8. The method according to claim 7, wherein the carbon source gas has a concentration of 5 to 50% in the mixed gas of the carbon source gas and the auxiliary gas.
9. The method according to claim 2, wherein the group modification in step S3 is one of hydroxylation modification, oxidation modification, acidification modification and alkalization modification.
10. The method of claim 9, wherein the hydroxylation modification is performed using a resin or PVP; carrying out oxidation modification by using oxygen or hydrogen peroxide; carrying out acidification modification by using oxalic acid, acetic acid or carbonic acid; and (3) carrying out alkalization modification by adopting sodium hydroxide or potassium hydroxide.
11. A positive electrode material obtained by sintering the precursor material according to claim 1 mixed with lithium.
12. The positive electrode material according to claim 11, wherein the sintering temperature is 700 to 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 according to claim 13, wherein a carbon layer is coated on the surface of the positive electrode material by: and (3) placing the anode material in a CVD furnace, introducing protective gas, then introducing carbon source gas and auxiliary gas, and heating and preserving heat for a period of time.
15. The positive electrode material according to claim 14, wherein the CVD furnace is a static furnace; the temperature of the heat preservation is 900 to 1200 ℃; the heating rate during heating is 1 to 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 true CN115259242A (en) | 2022-11-01 |
| CN115259242B 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 (12)
| 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 |
| US20160285086A1 (en) * | 2013-11-08 | 2016-09-29 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method of manufacturing an electrode material, electrode material and vehicle comprising a battery including such an electrode material |
| US20170317344A1 (en) * | 2014-10-30 | 2017-11-02 | Institute Of Process Engineering, Chinese Academy Of Sciences | Nickel lithium ion battery positive electrode material having concentration gradient, and preparation method therefor |
| 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 |
| US20210367233A1 (en) * | 2018-08-28 | 2021-11-25 | Byd Company Limited | Ternary positive electrode material and preparation method therefor, and lithium-ion battery |
| 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 |
-
2022
- 2022-08-19 CN CN202210996562.0A patent/CN115259242B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160285086A1 (en) * | 2013-11-08 | 2016-09-29 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method of manufacturing an electrode material, electrode material and vehicle comprising a battery including such an electrode material |
| 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 |
| US20170317344A1 (en) * | 2014-10-30 | 2017-11-02 | Institute Of Process Engineering, Chinese Academy Of Sciences | Nickel lithium ion battery positive electrode material having concentration gradient, and preparation method therefor |
| 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 |
| US20210367233A1 (en) * | 2018-08-28 | 2021-11-25 | Byd Company Limited | Ternary positive electrode material and preparation method therefor, 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 |
|---|
| BEIBEI WANG: "Synthesis and electrochemical investigation of core-shell ultrathin NiO nanosheets grown on hollow carbon microspheres composite for high performance lithium and sodium ion batteries", CHEMICAL ENGINEERING JOURNAL * |
| HENGRUI QIU: "MWCNTs-GONRs/Co3O4@Ni(OH)2core-shell array structure with a high performance electrode for supercapacitor", CHEMICAL ENGINEERING JOURNAL * |
| 郑朝晖;李凤岐;安玉良;袁霞;张罡;: "碳包覆Ni/Y_2O_3纳米颗粒的制备与表征", 辽宁化工 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115259242B (en) | 2023-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110233250B (en) | Preparation method of single crystal particle ternary cathode material | |
| CN111082006B (en) | Silicon monoxide composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN111446445A (en) | Plasma treatment method for nickel-based lithium ion positive electrode material precursor | |
| CN112349885A (en) | Modified lithium ion battery positive electrode material and preparation method thereof | |
| CN109286001A (en) | A kind of modified lithium nickelate preparation method | |
| CN115241450A (en) | Preparation and application of doped sodium ion nickel-iron-manganese-based single crystal battery positive electrode material | |
| CN114702022B (en) | Preparation method and application of hard carbon anode material | |
| CN112499631A (en) | Fe3C/C composite material and application thereof | |
| CN115520904A (en) | Positive electrode material precursor, preparation method thereof and positive electrode material | |
| CN114275762B (en) | Nitrogen-doped hard carbon sodium ion battery anode material and preparation method thereof | |
| CN114772658A (en) | Precursor of power type lithium ion battery anode material and preparation method thereof | |
| CN116344731A (en) | Core-shell structure type sodium ion battery anode material and preparation method thereof | |
| CN114597378A (en) | Ultrahigh nickel polycrystalline positive electrode material and preparation method and application thereof | |
| CN114204011A (en) | Preparation method of nickel cobalt lithium manganate ternary cathode material | |
| CN117219740A (en) | Doped modified sodium ion battery positive electrode material and preparation method thereof | |
| CN115312736B (en) | Preparation method of Si@TiN-asphalt composite anode material | |
| CN115140783B (en) | Ternary positive electrode material precursor, and preparation method and application thereof | |
| CN115259242B (en) | Carbon-based precursor material, positive electrode material and preparation method | |
| CN110993917B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN113690415A (en) | Long-storage positive electrode material and preparation method thereof | |
| CN114314553A (en) | Modified lithium iron phosphate, preparation method thereof and lithium ion battery | |
| CN114105149A (en) | Carbon-coated nitrogen-phosphorus double-doped silicon monoxide composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN111653765A (en) | Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material | |
| CN115477337B (en) | Preparation method of precursor with high specific surface area and high tap density | |
| CN114262955B (en) | Size-controllable Ni-NiO heterojunction nanoparticle doped carbon fiber, preparation method and application thereof in lithium-sulfur battery diaphragm |
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 |