CN115231622A - Method for preparing manganese cobalt oxygen by inducing low-temperature heat treatment of nanofiber template - Google Patents
Method for preparing manganese cobalt oxygen by inducing low-temperature heat treatment of nanofiber template Download PDFInfo
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- CN115231622A CN115231622A CN202210789291.1A CN202210789291A CN115231622A CN 115231622 A CN115231622 A CN 115231622A CN 202210789291 A CN202210789291 A CN 202210789291A CN 115231622 A CN115231622 A CN 115231622A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
- H01M2004/027—Negative electrodes
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- 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 provides a method for preparing manganese, cobalt and oxygen by inducing low-temperature heat treatment of a nanofiber template. Dissolving polyvinylidene fluoride in a solvent, and heating the solution until the polyvinylidene fluoride is completely dissolved; adding soluble cobalt salt and manganese salt into the solution, continuously stirring until a uniform solution is formed, and preparing the PVDF/(cobalt salt + manganese salt) nano fibrofelt by adopting an electrostatic spinning method; and the distance between the receiving plate and the spinning end is 10-15 cm; and (3) carrying out low-temperature treatment on the PVDF/(cobalt salt and manganese salt) nano fiber felt for 12-24 h at 140-180 ℃, and then calcining for 2-4 h at 350-370 ℃ to obtain manganese-cobalt-oxygen nano powder. The average specific discharge capacity of the composite material is about 1089 mAh/g under the current density of 200 mA/g, about 896 mAh/g under the current density of 400 mA/g, about 744 mAh/g under the current density of 1000 mA/g, and about 965 mAh/g when the composite material returns to the current density of 200 mA/g.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery cathode material, in particular to a method for preparing manganese, cobalt and oxygen by inducing low-temperature heat treatment of a nanofiber template, and belongs to the field of new energy materials.
Background
With the progress of technology, lithium ion batteries are widely applied to the fields of electric automobiles, aerospace, biomedicine and the like, so that the research and development of lithium ion batteries for power and related materials have great significance. For the lithium ion battery for power, the key is to improve the power density and the energy density, and the improvement of the power density and the energy density is the improvement of an electrode material, particularly a negative electrode material.
Carbon materials are the materials which are researched and applied to commercialization of lithium ion batteries at the earliest time and still remain one of the important points of attention and research, but carbon negative electrode materials have some defects: reacts with the electrolyte to form an SEI film, resulting in consumption of the electrolyte and lower first coulombic efficiency; when the battery is overcharged, metal lithium may be separated out on the surface of the carbon electrode to form lithium dendrite to cause short circuit, so that the temperature is increased, and the battery explodes; in addition, the diffusion coefficient of lithium ions in the carbon material is small, so that the battery cannot realize large-current charging and discharging, and the application range of the lithium ion battery is limited.
Mn-Co-O Mn 2 CoO 4 Is a spinel-structured composite oxide, is a widely applied magnetic material, can be used as a lithium ion battery cathode material at present, and has higher Li content through conversion and alloying reactions + A storage capacity. The material is considered to be a promising lithium ion negative electrode material. However, the application of the material is limited by the defects of large volume change, low conductivity and the like in the charging and discharging processes.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing manganese, cobalt and oxygen by inducing low-temperature heat treatment on a nanofiber template, which has a relatively simple process and is easy to operate. So as to obtain smaller nano particles with larger specific surface area, thereby improving the electrochemical performance of the material.
The invention aims to realize the following scheme, and the method for preparing manganese cobalt oxide by inducing low-temperature heat treatment of the nanofiber template comprises the following steps:
(1) Dissolving polyvinylidene fluoride (PVDF) in a mixed solvent of N, N-dimethylformamide and acetone, wherein the volume ratio of the N, N-dimethylformamide to the acetone is (1-3): 1; heating the solution to 50-55 ℃ until the PVDF is completely dissolved;
(2) Adding soluble cobalt salt and manganese salt into the solution, wherein the molar weight ratio of the cobalt salt to the manganese salt is 1:2, continuously stirring the mixture until a uniform solution is formed, and preparing the PVDF/(cobalt salt and manganese salt) nano fibrofelt by adopting an electrostatic spinning method under the voltage of 10-15 KV; and the distance between the receiving plate and the spinning end is 10-15 cm;
(3) And (2) treating the PVDF/(cobalt salt + manganese salt) nano fiber felt at low temperature, carrying out heat treatment for 12-24 h at 140-180 ℃, and calcining for 2-4 h at 350-370 ℃ to obtain PVDF/manganese cobalt oxide nano powder.
The soluble cobalt salt is one or the combination of cobalt acetate, cobalt citrate or cobalt lactate.
The manganese salt is one or the combination of manganese acetate, manganese citrate or manganese lactate.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a method for preparing manganese, cobalt and oxygen by inducing low-temperature heat treatment of a nanofiber template, and nanoparticles prepared by the method have larger specific surface area and play an important role in improving the electrochemical performance of materials. Is favorable for improving the electrochemical performance of the material. The preparation process is relatively simple and easy to operate. The average specific discharge capacity was about 1089 mAh/g at a current density of 200 mA/g, about 896 mAh/g at a current density of 400 mA/g, about 744 mAh/g at a current density of 1000 mA/g, and about 965 mAh/g when returned to the current density of 200 mA/g.
Drawings
FIG. 1 is a graph of the cycle rate life performance of manganese, cobalt and oxygen in example 1.
Detailed Description
The present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1
Manganese cobalt oxide prepared by inducing low-temperature heat treatment of a nanofiber template is prepared by the following steps,
(1) Dissolving polyvinylidene fluoride in a mixed solvent of N, N-dimethylformamide and acetone, wherein the volume ratio of the N, N-dimethylformamide to the acetone is 1:1; heating the solution to 50 ℃ until the polyvinylidene fluoride is completely dissolved;
(2) Adding soluble cobalt acetate and manganese acetate into the solution, wherein the molar weight ratio of the cobalt acetate to the manganese acetate is 1 mmol:2 mmol, continuously stirring to form a uniform solution, and preparing the PVDF/(cobalt acetate + manganese acetate) nano fiber felt by an electrostatic spinning method under the voltage of 10-15 KV; and the distance between the receiving plate and the spinning end is 10 cm;
(3) And (3) performing low-temperature treatment on the PVDF/(cobalt acetate + manganese acetate) nano-fiber felt at 140 ℃ for 24 hours, and calcining at 370 ℃ for 2 hours to obtain manganese-cobalt-oxygen nano-powder.
FIG. 1 is a graph showing the cycle rate life performance of Mn, co and O in this example, wherein the average specific discharge capacity is 1089 mAh/g at a current density of 200 mA/g, about 896 mAh/g at a current density of 400 mA/g, about 744 mAh/g at a current density of 1000 mA/g, and about 965 mAh/g when the current density returns to 200 mA/g.
Example 2
Manganese cobalt oxide prepared by inducing low-temperature heat treatment of a nanofiber template is prepared by the following steps,
(1) Dissolving polyvinylidene fluoride in a mixed solvent of N, N-dimethylformamide and acetone, wherein the volume ratio of the N, N-dimethylformamide to the acetone is 2:1; heating the solution to 55 ℃ until the polyvinylidene fluoride is completely dissolved;
(2) Adding soluble cobalt citrate and manganese citrate into the solution, wherein the molar weight ratio of the cobalt citrate to the manganese citrate is 1 mmol:2 mmol, continuously stirring the mixture until a uniform solution is formed, and preparing the PVDF/(cobalt citrate + manganese citrate) nano fiber felt by adopting an electrostatic spinning method under the voltage of 15 KV; and the distance between the receiving plate and the spinning end is 15 cm;
(3) And (3) performing low-temperature treatment on the PVDF/(cobalt citrate + manganese citrate) nano fiber felt, performing heat treatment at 160 ℃ for 20 hours, and calcining at 360 ℃ for 3 hours to obtain manganese-cobalt-oxygen nano powder.
Example 3
Manganese cobalt oxygen prepared by inducing low-temperature heat treatment of a nanofiber template is prepared by the following steps,
(1) Dissolving polyvinylidene fluoride in a mixed solvent of N, N-dimethylformamide and acetone, wherein the volume ratio of the N, N-dimethylformamide to the acetone is 3:1; heating the solution to 55 ℃ until the polyvinylidene fluoride is completely dissolved;
(2) Adding soluble cobalt lactate and manganese lactate into the solution, wherein the molar weight ratio of the cobalt lactate to the manganese lactate is 1 mmol:2 mmol, continuously stirring the mixture until a uniform solution is formed, and preparing the PVDF/(cobalt lactate + manganese lactate) nano fibrofelt by an electrostatic spinning method under the voltage of 15 KV; and the distance between the receiving plate and the spinning end is 15 cm;
(3) And (3) carrying out low-temperature treatment on the PVDF/(cobalt lactate + manganese lactate) nano fiber felt for 12 h at 180 ℃, and then calcining for 4 h at 350 ℃ to obtain manganese-cobalt-oxygen nano powder.
Claims (3)
1. A method for preparing manganese cobalt oxide by inducing low-temperature heat treatment of a nanofiber template is characterized by comprising the following steps,
(1) Dissolving polyvinylidene fluoride in a mixed solvent of N, N-dimethylformamide and acetone, wherein the volume ratio of the N, N-dimethylformamide to the acetone is 1-3:1; heating the solution to 50-55 ℃ until the polyvinylidene fluoride is completely dissolved;
(2) Adding soluble cobalt salt and manganese salt into the solution, wherein the molar weight ratio of the cobalt salt to the manganese salt is 1:2, continuously stirring the mixture until a uniform solution is formed, and preparing the PVDF/(cobalt salt and manganese salt) nano fibrofelt by adopting an electrostatic spinning method under the voltage of 10-15 KV; and the distance between the receiving plate and the spinning end is 10-15 cm;
(3) And (3) carrying out low-temperature treatment on the PVDF/(cobalt salt and manganese salt) nano fiber felt for 12-24 h at 140-180 ℃, and then calcining for 2-4 h at 350-370 ℃ to obtain manganese-cobalt-oxygen nano powder.
2. The method for preparing Mn-Co-O by the nanofiber template-induced low-temperature heat treatment as claimed in claim 1, wherein the cobalt salt is one or a combination of cobalt acetate, cobalt citrate or cobalt lactate.
3. The method for preparing manganese cobalt oxide by the induction of low-temperature heat treatment on the nanofiber template as claimed in claim 1, wherein the manganese salt is one or a combination of cobalt acetate, cobalt citrate or cobalt lactate.
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Cited By (1)
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CN115504527A (en) * | 2022-11-09 | 2022-12-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing ternary nano material by inducing nanofiber template, product and application |
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